CN1098763C

CN1098763C - Process for molding synthetic resins

Info

Publication number: CN1098763C
Application number: CN96196764A
Authority: CN
Inventors: 片冈纮; 梅井勇雄; 加藤严生
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 1995-07-25
Filing date: 1996-07-24
Publication date: 2003-01-15
Anticipated expiration: 2016-07-24
Also published as: MY141391A; WO1997004938A1; CN1195312A

Abstract

A process for molding a synthetic resin, characterized by conducting the molding (1) by the use of a main metal mold constituting a mold cavity covered with a heat insulating layer in a state closely adherent to the mold surface in which a heat insulating layer made of a heat-resistant polymer having a thickness of more than 0.1 mm but below 0.5 mm covers the mold surface, and a metal layer covers the heat insulating layer in a state closely adherent to the insulating layer, (2) under the conditions that the integral [(mold surface temp.)-(softening temp. of the synthetic resin)] value ( DELTA H) over the period in which the mold surface temperature equals or exceeds the softening temperature of the synthetic resin after the point of time when the resin to be molded has come into contact with the mold surface is 2 sec. DEG C or above, and/or that the integral [mold surface temp.-(softening temp. of the synthetic resin - 10 DEG C)] value ( DELTA h) over the period in which the mold surface temperature equals or exceeds the softening temperature ( DEG C) of the synthetic resin minus 10 after the above point of time is 5 sec. DEG C or above, and (3) under the condition that the mold surface temperature lowers to the softening temperature of the resin or below after 5 seconds from the point of time when the resin to be molded has come into contact with the mold surface.

Description

The forming method of synthetic resin

Technical field

The present invention relates to the forming method of synthetic resin.In more detail, the invention provides the forming method of a kind of injection mo(u)lding that is suitable for synthetic resin, blow molding etc.In recent years, strong day by day to saving the requirement that back processing such as on the injection-molded item of synthetic resin or blow-molded article, applies.That is, in order to reduce the utilizing again of manufacturing cost, moulded products, to reduce environmental disruption that solvent evaporation when applying etc. causes etc., an urgent demand does not apply.Particularly the back processing of synthetic resin system shells such as electric machine, electronic instrument, office equipment etc. is saved in strong request.The invention provides a kind of forming method that can satisfy these requirements economically.

Background technology

Thermoplastic injection is come moulding in mold cavity, in order to improve the repeatability that moulded products has die surface shape state, improve the outward appearance of moulded products, usually can be by select improving resin temperature or mold temperature, or improving condition of molding such as injection pressure reaches to a certain degree.Blow molding in order to improve the outward appearance of moulded products, can improve resin temperature or mold temperature by selection too usually, or improving conditions of molding such as being blown into gas pressure reaches to a certain degree.

What have the greatest impact in these factors is mold temperature, and mold temperature is high more good more.But if the mold temperature height, then the cooling curing of plasticization resin is long required cool time, and shaping efficiency reduces.Require a kind of mold temperature that do not improve to improve the die surface repeatability, even perhaps improve the method that mold temperature also can not prolong necessary cool time.

" plastics technology " (Plastic Technology6 month, p.151 (1988)) etc. in illustrated a kind of hole that heating and cooling use is installed respectively on mould, alternately feeding heat transfer medium and cooling agent comes the method for heating and cooling mould repeatedly, but this method heat consumption is big, and cool time is long.

A kind of die cavity wall is disclosed with the little material of thermal conductivity, the mould of promptly thin heat insulation layer lining among the WO93/06980 etc.

In addition, United States Patent (USP) 3,734,449, die cavity wall that a kind of mould has been shown in each specification of United States Patent (USP) 5,302,467 and United States Patent (USP) 5,388,803 with thin heat insulation layer lining, its surface again with the mould of thin metal layer lining.But the unexposed while is fully satisfied the forming method of die surface repeatability and molding cycle time in these known documents.

In the past, the die surface repeatability during moulding is opposite with the effect of molding cycle time.That is, if the mold temperature height, then the repeatability of die surface is good, but the molding cycle time is long.Use under the occasion of heat insulation layer lining mould, perhaps on the heat insulation layer surface again in the heat insulation layer of the coated metal layer lining mould, if adiabatic bed thickness, then the repeatability of die surface is good, but the molding cycle time is long, if the outermost metal bed thickness, then the repeatability of die surface is poor.Past die surface repeatability and molding cycle time relation are either-ors, and problem of the present invention makes the two compatibility exactly.

In order to make die surface repeatability and the two compatibility of molding cycle time, use heat insulation layer lining mould, adopt under the occasion of polymer as heat insulation layer, generally in use heat insulation layer easily is scratched, and when adding inorganic filling material in a large number in the synthetic resin, die surface is easier to be scratched.And under some occasion, owing to by the difference of the kind of shaping synthetic resin, be difficult to the demoulding from mould sometimes when moulding, people require this improvement.As this improvement method, consider on the heat insulation layer surface, to be covered thin metal layer.

The invention provides a kind of like this forming method, this method is used the mould of the metal level of lining limited range on the outermost layer of the heat insulation layer lining mould of limited range, carry out moulding with the condition of molding that limits, can satisfy die surface repeatability, molding cycle time and mould durability three.

Also there is variety of issue in the mould of lining thin metal layer on the heat insulation layer surface, and we find to have following problem.Comprise, if the relation of metal layer thickness and heat insulation layer thickness is incorrect, then the repeatability of die surface is bad during moulding, if heat insulation layer thickness is big, then the molding cycle time is long, shaping efficiency reduces, if metal bed thickness, then the repeatability of die surface is poor, necessary heat insulation layer thickness and metal layer thickness and by the softening temperature of the synthetic resin of moulding, condition of molding such as mold temperature and resin temperature etc. has confidential relation, the driving fit securely of metal level and heat insulation layer, and the closed surface of heat insulation layer and metal level must tolerate the colding and heat succeed each other repeatedly of being caused by molding synthetic resin, surface metal-layer must have durability, needs special durability when particularly being added inorganic filling material in the synthetic resin of moulding, and these problems must solve.

Disclosure of an invention

Present inventors are in order to address these problems, studied the mould of lining heat insulation layer, discussed and the adiabatic material of the main die surface that is covered and thickness thereof, its lining state, and the combination of main mold material, and the closing force of the metal level of outermost layer lining and thickness thereof, by the relation between the condition of molding of the softening temperature of the synthetic resin of moulding, synthetic resin, die surface repeatability, molding cycle time and the mould durability three of moulded products are met, so far finish the present invention.

That is, the present invention is as follows.

1. the forming method of a synthetic resin comprises

(1) uses a kind of heat insulation layer lining mould, it is on the die surface that constitutes metal system master mold cavity, exist the heat insulation layer that forms by heat resistant polymer with the 0.1mm～0.5mm of this die surface driving fit, and exist the metal level of driving fit on the above-mentioned heat insulation layer

And the following condition of molding moulding of employing:

(2) by the synthetic resin of moulding with after die surface contacts, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the integrated value (Δ H) of the value of (mold surface temperature-synthetic resin softening temperature) is more than 2 seconds ℃, and/or, be equal to or higher than at mold surface temperature during (synthetic resin softening temperature-10 ℃), the integrated value (Δ h) of the value of { mold surface temperature-(synthetic resin softening temperature-10 ℃) } is more than 10 seconds ℃, and

(3) contacted 5 seconds with die surface by the synthetic resin of moulding after, mold surface temperature is reduced to below the synthetic resin softening temperature.

2. the injection molding forming method of a synthetic resin comprises

(1) uses a kind of heat insulation layer lining mould, it is on the die surface that constitutes metal system master mold cavity, exist the heat insulation layer that forms by heat resistant polymer with the 0.1mm～0.5mm of this die surface driving fit, and existing 1/3 and the thickness that are lower than heat insulation layer thickness on the above-mentioned heat insulation layer is the metal level of 0.001～0.1mm

And the following condition of molding moulding of employing:

(2) main mold temperature is set in 15 ℃～100 ℃ and be lower than 20 ℃ of synthetic resin softening temperatures temperature and

(3) by the synthetic resin of moulding with after die surface contacts, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the integrated value (Δ H) of the value of (mold surface temperature-synthetic resin softening temperature) is more than 2 seconds ℃, and/or, be equal to or higher than at mold surface temperature during (synthetic resin softening temperature-10 ℃), the integrated value (Δ h) of the value of { mold surface temperature-(synthetic resin softening temperature-10 ℃) } is more than 10 seconds ℃, and

(4) contacted 5 seconds with die surface by the synthetic resin of moulding after, mold surface temperature is reduced to below the synthetic resin softening temperature.

3. the injection molding forming method of a synthetic resin comprises

(1) uses a kind of heat insulation layer lining mould, it is on the die surface that constitutes metal system master mold cavity, exist the heat insulation layer that forms by heat resistant polymer with the 0.1mm～0.5mm of this die surface driving fit, and exist metal level on the above-mentioned heat insulation layer with textured surface, the protuberance metal layer thickness be lower than heat insulation layer thickness 1/3 and be 0.01～0.1mm, concave depth is 0.001～0.09mm, and less than protuberance thickness

And the following condition of molding moulding of employing:

4. the injection molding forming method of the synthetic resin of record in above-mentioned 2, wherein, heat insulation layer thickness is 0.1mm～0.4mm, metal layer thickness be lower than heat insulation layer thickness 1/3 and be 0.001～0.07mm, and adopt a kind of like this condition of molding injection mo(u)lding, promptly, integrated value (Δ H) is 2 seconds ℃～50 seconds ℃, and/or integrated value (Δ h) is 10 seconds ℃～100 seconds ℃, and after synthetic resin contacted 5 seconds with die surface, and mold surface temperature is reduced to below (synthetic resin softening temperature-10 ℃).

5. the injection molding forming method of the synthetic resin of record in above-mentioned 2, wherein, heat insulation layer thickness is 0.12mm～0.3mm, and metal layer thickness is 1/100～1/5 of a heat insulation layer thickness, and is 0.002～0.06mm, and a kind of like this condition of molding injection mo(u)lding of employing, that is, integrated value (Δ H) is 5 seconds ℃～40 seconds ℃, and/or integrated value (Δ h) is 12 seconds ℃～70 seconds ℃, and after synthetic resin contacted 5 seconds with die surface, mold surface temperature was reduced to below (synthetic resin softening temperature-10 ℃).

6. the injection molding forming method of the synthetic resin of record in above-mentioned 3, wherein, heat insulation layer thickness is 0.1mm～0.4mm, the protuberance metal layer thickness is lower than 1/3 of heat insulation layer thickness, and be 0.01～0.07mm, the recess depths of decorative pattern shape is 0.005～0.06mm, and a kind of like this condition of molding injection mo(u)lding of employing, promptly, integrated value (Δ H) is 2 seconds ℃～50 seconds ℃, and/or integrated value (Δ h) is 10 seconds ℃～100 seconds ℃, and after synthetic resin contacted 5 seconds with die surface, and mold surface temperature is reduced to below (synthetic resin softening temperature-10 ℃).

7. the injection molding forming method of the synthetic resin of record in above-mentioned 3, wherein, heat insulation layer thickness is 0.12mm～0.3mm, the protuberance metal layer thickness is lower than 1/5 of heat insulation layer thickness, and be 0.01～0.06mm, the recess depths of decorative pattern shape is 0.005～0.04mm, and a kind of like this condition of molding injection mo(u)lding of employing, promptly, integrated value (Δ H) is 5 seconds ℃～40 seconds ℃, and/or integrated value (Δ h) is 12 seconds ℃～70 seconds ℃, and after synthetic resin contacted 5 seconds with die surface, and mold surface temperature is reduced to below (synthetic resin softening temperature-10 ℃).

8. the injection molding forming method of the synthetic resin of record in above-mentioned 2,3,4,5,6 or 7, adopting synthetic resin average flow velocity in mould is 20～300mm/ condition injection mo(u)lding of second.

9. the blow molding method of a synthetic resin comprises

(1) uses a kind of heat insulation layer lining mould, it is on the die surface that constitutes metal system master mold cavity, exist heat insulation layer with the 0.1mm～0.5mm that forms by heat resistant polymer of this die surface driving fit, and existing 1/3 and the thickness that are lower than heat insulation layer thickness on the above-mentioned heat insulation layer is the metal level of 0.002～0.1mm

And the following condition of molding moulding of employing:

(2) main mold temperature is set in 15 ℃～100 ℃, and be lower than 20 ℃ of synthetic resin softening temperatures temperature and

(3) by the synthetic resin of moulding with after die surface contacts, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the integrated value (Δ H) of the value of (mold surface temperature-synthetic resin softening temperature) is 10 seconds ℃～200 seconds ℃, and/or, be equal to or higher than at mold surface temperature during (synthetic resin softening temperature-10 ℃), the integrated value (Δ h) of the value of { mold surface temperature-(synthetic resin softening temperature-10 ℃) } is 20 seconds ℃～400 seconds ℃, and

10. the blow molding method of the synthetic resin of record in above-mentioned 9, wherein, heat insulation layer thickness is 0.2mm～0.5mm, metal layer thickness is 1/100～1/5 of a heat insulation layer thickness, and be 0.004～0.06mm, and adopt a kind of like this condition of molding blow molding, promptly, integrated value (Δ H) is 20 seconds ℃～100 seconds ℃, and/or integrated value (Δ h) is 30 seconds ℃～300 seconds ℃.

11. the blow molding method of a synthetic resin comprises

(1) uses a kind of heat insulation layer lining mould, it is on the die surface that constitutes metal system master mold cavity, exist heat insulation layer with the 0.1mm～0.5mm that forms by heat resistant polymer of this die surface driving fit, and exist metal level on the above-mentioned heat insulation layer with textured surface, the protuberance metal layer thickness be lower than heat insulation layer thickness 1/3 and be 0.01～0.1mm, concave depth is 0.005～0.09mm

And the following condition of molding moulding of employing:

12. the forming method of the synthetic resin of record in above-mentioned 11, wherein, heat insulation layer thickness is 0.2mm～0.5mm, the protuberance metal layer thickness is 1/100～1/5 of a heat insulation layer thickness, and is 0.01～0.08mm, and the recess depths of decorative pattern shape is 0.005～0.07mm, and a kind of like this condition of molding blow molding of employing, that is, integrated value (Δ H) is 20 seconds ℃～100 seconds ℃, and/or integrated value (Δ h) is 30 seconds ℃～300 seconds ℃.

13. the blow molding method of the synthetic resin described in above-mentioned 9,10,11 or 12, wherein, from parison contact with die surface to the time that blow molding pressure is full of moulded products inside fully be 1～5 second, with this condition blow molding.

14. the forming method of the synthetic resin described in above-mentioned 1,2,3,4,5,6,7,8,9,10,11,12 or 13, wherein, heat insulation layer and metal level are with the driving fit of micro concavo-convex interface.

15. the forming method of the synthetic resin described in above-mentioned 1,2,3,4,5,6,7,8,9,10,11,12,13 or 14, wherein, the heat resistant polymer that forms heat insulation layer is made of straight chain polymer amount polyimides.

16. above-mentioned 1,2,3,4,5,6,7,8,9,10,11,12,13, the forming method of the synthetic resin described in 14 or 15, wherein, use a kind of like this mould of coated metal layer, promptly, form the heat insulation layer outermost layer with the heat resistant polymer that has added micronized etching auxiliary agent by 1～30 weight %, then, this heat insulation layer outermost layer is carried out chemical etching to be handled, form the micro concavo-convex shape, carry out chemical plating in its surface, carry out once above chemical plating and/or plating more as required, form metal level, the closing force of this metal level is more than the 0.3kg/10mm.

17. the forming method of the synthetic resin described in above-mentioned 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 or 16 wherein, uses layer on surface of metal or the part metals laminar surface mould as mirror-like.

18. the forming method of the synthetic resin described in above-mentioned 1,2,4,5,8,14,15 or 16, wherein, use layer on surface of metal or part metals laminar surface are the concavo-convex mould as lens.

19. the forming method of the synthetic resin described in above-mentioned 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 or 16 wherein, uses layer on surface of metal or the part metals laminar surface mould as micro concavo-convex delustring shape.

20. the forming method of the synthetic resin described in above-mentioned 1,3,6,7,8,11,12,13,14,15 or 16 wherein, uses either party in the protuberance of layer on surface of metal and the recess to be mirror-like, the opposing party mould as the delustring shape.

21. the forming method of the synthetic resin described in above-mentioned 19 or 20, wherein, use layer on surface of metal or part metals laminar surface have the mould through the delustring shape surface of multistage blasting treatment and/or the formation of multistage etch processes.

22. the forming method of the synthetic resin described in above-mentioned 21 wherein, uses the mould have 2 layers of metal level at least, the hardness of mold cavity side surface metal level less than its inboard metal level and/or etching greater than its inboard metal level.

23. the forming method of the synthetic resin described in above-mentioned 22, wherein, use a kind of like this mould, promptly, the etching speed of the mold cavity side surface metal level of metal level is more than 2 times of its inboard metal level etching speed, and above-mentioned metal level forms delustring shape surface through multistage etch processes.

24. the forming method of the synthetic resin described in above-mentioned 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22 or 23, wherein, the synthetic resin of moulding is the non-crystalline resin that is selected from methacrylate resins such as phenylethylene resin series such as polystyrene, polystyrene rubber reinforcement, SAN, ABS resin, styrene-methylmethacrylate copolymer, polymethyl methacrylate, rubber enhancing polymethyl methacrylate, Merlon.

25. the forming method of the synthetic resin described in above-mentioned 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23 or 24, wherein, synthetic resin is the synthetic resin that contains inorganic filling materials such as 5～65 weight % are fibrous, Powdered, uses the hardness mould identical or higher with the hardness of inorganic filling material in the synthetic resin of mould outermost metal layer.

26. the forming method of the synthetic resin described in above-mentioned 25, wherein, synthetic resin contains 20 weight %～65 weight % inorganic filling materials.

27. the forming method of the synthetic resin described in above-mentioned 25, wherein, synthetic resin contains 30～50 weight % inorganic filling materials.

Simple declaration to accompanying drawing

When Fig. 1 contacted with steel master mould for heated synthetic resin is shown, near the synthetic resin Temperature Distribution the die surface changed the curve map of (calculated value).

Fig. 2 is when heated synthetic resin being shown contact with the mould of lining 0.1mm polyimides on the die surface of steel master mould, the curve map of near synthetic resin the die surface and the Temperature Distribution of heat-resistant resin variation (calculated value).

Fig. 3 is when heated synthetic resin being shown contact with the mould of lining 0.3mm polyimides on the die surface of steel master mould, the curve map of near synthetic resin the die surface and the Temperature Distribution of heat-resistant resin variation (calculated value).

Fig. 4 is when heated synthetic resin being shown contacting with the mould of lining all thickness polyimides on the die surface of steel master mould, and mold surface temperature changes the curve map of (calculated value) in time.

Fig. 5 is for being illustrated under various resin temperatures and the mold temperature, and when synthetic resin contacted with the mould of lining 0.2mm thick polyimide on the die surface of steel master mould, mold surface temperature changed the curve map of (calculated value) in time.

Fig. 6 is for being illustrated under various moulded products thickness and the mold temperature, and when synthetic resin contacted with the mould of lining 0.2mm thick polyimide on the die surface of steel master mould, mold surface temperature changed the curve map of (calculated value) in time.

Fig. 7 be illustrate heated synthetic resin with lining 0.3mm polyimides on the die surface of steel master mould, be covered the mould of 0.02mm nickel in its surface when contacting again, the curve map of die surface (interface of resin surface and die surface) variations in temperature (calculated value).

Fig. 8 illustrates heated synthetic resin with lining 0.3mm polyimides on the die surface of steel master mould, be covered the mould of all thickness nickel dam in its surface when contacting again, and die surface (interface of resin surface and die surface) temperature changes the curve map of (calculated value) in time.

Fig. 9 is polystyrene rubber reinforcement (HIPS) for being illustrated in synthetic resin, moulded products thickness is 2mm, the synthetic resin temperature is 240 ℃, main mold temperature is 50 ℃, nickel layer thickness is under the condition of 0.03mm, make the polyimides layer thickness change into 0.1mm, 0.2mm, 0.3mm, 0.5mm carry out under the occasion of moulding, mold surface temperature time history plot (9-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (9-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 10 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, the synthetic resin temperature is 240 ℃ and 270 ℃, main mold temperature is 30 ℃, nickel layer thickness is under the condition of 0.05mm, make the polyimides layer thickness change into 0.1mm, 0.2mm carry out under the occasion of moulding, mold surface temperature time history plot (10-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (10-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 11 is that to be illustrated in synthetic resin be that HIPS, moulded products thickness are that 2mm, synthetic resin temperature are that 240 ℃, main mold temperature are that 70 ℃, nickel layer thickness are under the condition of 0.03mm, the polyimides layer thickness is changed under the occasion that 0.1mm, 0.2mm carry out moulding, mold surface temperature time history plot (11-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (11-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 12 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, the synthetic resin temperature is 240 ℃, main mold temperature is 50 ℃, nickel layer thickness is 0.01mm, 0.02mm condition under, make the polyimides layer thickness change into 0.2mm, 0.3mm carry out under the occasion of moulding, mold surface temperature time history plot (12-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (12-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 13 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, the synthetic resin temperature is 240 ℃, main mold temperature is 50 ℃, the polyimides layer thickness is under the condition of 0.3mm, make nickel layer thickness change into 0.01mm, 0.02mm, 0.03mm, 0.05mm, 0.1mm carry out under the occasion of moulding, mold surface temperature time history plot (13-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (13-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 14 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, the synthetic resin temperature is 240 ℃, main mold temperature is 50 ℃, the polyimides layer thickness is under the condition of 0.2mm, make nickel layer thickness change into 0.02mm, 0.03mm, 0.05mm carry out under the occasion of moulding, mold surface temperature time history plot (14-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (14-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 15 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, the synthetic resin temperature is 240 ℃, main mold temperature is 30 ℃, the polyimides layer thickness is under the condition of 0.2mm, make nickel layer thickness change into 0.01mm, 0.02mm, 0.03mm carry out under the occasion of moulding, mold surface temperature time history plot (15-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (15-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 16 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, the synthetic resin temperature is 240 ℃, nickel layer thickness is 0.01mm, the polyimides layer thickness is under the condition of 0.1mm, make main mold temperature change into 30 ℃, 40 ℃, under the occasion that 50 ℃ are carried out moulding, mold surface temperature time history plot (16-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (16-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 17 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, the synthetic resin temperature is 240 ℃, nickel layer thickness is 0.02mm, the polyimides layer thickness is under the condition of 0.1mm, make main mold temperature change into 30 ℃, 40 ℃, 50 ℃, under the occasion that 70 ℃ are carried out moulding, mold surface temperature time history plot (17-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (17-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 18 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, main mold temperature is 30 ℃, nickel layer thickness is 0.01mm, the polyimides layer thickness is under the condition of 0.1mm, making the synthetic resin temperature change is 210 ℃, 240 ℃, under the occasion that 270 ℃ are carried out moulding, mold surface temperature time history plot (18-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (18-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 19 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, main mold temperature is 30 ℃, the polyimides layer thickness is 0.1mm, nickel layer thickness is under the condition of 0.02mm, making the synthetic resin temperature change is 210 ℃, 240 ℃, under the occasion that 270 ℃ are carried out moulding, mold surface temperature time history plot (19-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (19-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 20 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, main mold temperature is 30 ℃, the polyimides layer thickness is 0.2mm, nickel layer thickness is under the condition of 0.01mm, making the synthetic resin temperature change is 210 ℃, 240 ℃, under the occasion that 270 ℃ are carried out moulding, mold surface temperature time history plot (20-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (20-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 21 is HIPS for being illustrated in synthetic resin, moulded products thickness is 2mm, main mold temperature is 30 ℃, the polyimides layer thickness is 0.2mm, nickel layer thickness is under the condition of 0.02mm, making the synthetic resin temperature change is 210 ℃, 240 ℃, under the occasion that 270 ℃ are carried out moulding, mold surface temperature time history plot (21-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (21-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 22 is HIPS for being illustrated in synthetic resin, the synthetic resin temperature is 240 ℃, main mold temperature is 50 ℃, the polyimides layer thickness is 0.2mm, nickel layer thickness is under the condition of 0.02mm, make moulded products thickness change into 3mm, 4mm, 5mm carries out under the occasion of moulding, mold surface temperature time history plot (22-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (22-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 23 is polyformaldehyde (POM) for being illustrated in synthetic resin, moulded products thickness is 2mm, the synthetic resin temperature is 200 ℃, main mold temperature is 60 ℃, the polyimides layer thickness is under the condition of 0.2mm, make nickel layer thickness change into 0.01mm, 0.02mm, 0.04mm carry out under the occasion of moulding, its surface temperature time history plot (23-A) of mould, and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (23-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 24 is POM for being illustrated in synthetic resin, moulded products thickness is 2mm, the synthetic resin temperature is 200 ℃, main mold temperature is 60 ℃, nickel layer thickness is under the condition of 0.02mm, make the polyimides layer thickness change into 0.2mm, 0.3mm, 0.4mm carry out under the occasion of moulding, mold surface temperature time history plot (24-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (24-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 25 is that to be illustrated in synthetic resin be that HIPS, moulded products thickness are that 3mm, heat-insulating material are that epoxy resin, heat insulation layer thickness are that 0.3mm, metal layer thickness are that 0.03mm, resin temperature are that 200 ℃, main mold temperature are the occasion of carrying out moulding under 40 ℃ the condition, and, be that HIPS, moulded products thickness are that 2mm, heat-insulating material are pottery (Y at synthetic resin ₂O ₃/ ZrO ₂), heat insulation layer thickness is that 0.3mm, no metal level, resin temperature are under 240 ℃ the condition, main mold temperature is changed under 35 ℃, the 50 ℃ occasions of carrying out moulding, mold surface temperature time history plot (25-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (25-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 26 is that to be illustrated in synthetic resin be that HIPS, moulded products thickness are that 2mm, polyimides layer thickness are that 0.5mm, nickel layer thickness are that 0.03mm, synthetic resin temperature are that 240 ℃ and 270 ℃, main mold temperature are to carry out under the occasion of moulding under the condition of 50 ℃ and 70 ℃, mold surface temperature time history plot (26-A), and, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map (26-B) of the relation of the integrated value (calculated value) of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature).

Figure 27 for mold surface temperature of the present invention change with the known document United States Patent (USP) of quoting 5,388,803 in the comparison diagram that changes of mold surface temperature shown in Figure 6.

Figure 28 illustrates the temperature variant curve map of thermal conductivity that is used to calculate the resin that mold surface temperature changes among each figure shown in the present.

Figure 29 illustrates the temperature variant curve map of specific heat that is used to calculate the resin that mold surface temperature changes among each figure shown in the present.

Figure 30 is the curve map that Mo Zhennei sheared heating when injection mo(u)lding was shown.

Figure 31 is that the glossiness of HIPS injection-molded item is with the curve map of resin temperature variation under the occasion that illustrates with the common die of no heat insulation layer and heat insulation layer lining mould.

Figure 32 is for during illustrating mold surface temperature and being equal to or higher than the synthetic resin softening temperature, by the curve map of glossiness with the relation of the integrated value (calculated value) of the value of (mold surface temperature-synthetic resin softening temperature) of the HIPS moulded products of heat insulation layer lining mold injection molding.

Figure 33 is equal to or higher than for mold surface temperature is shown during (synthetic resin softening temperature-10 ℃), the curve map of the glossiness of the HIPS moulded products of heat insulation layer lining mold injection molding and the relation of the integrated value (Δ h) of the value of { mold surface temperature-(synthetic resin softening temperature-10 ℃) }.

Figure 34 is for illustrating with under the occasion of common metal mould with HIPS (STYRON 495 Asahi Chemical Industries industry (strain) system trade name) injection mo(u)lding the curve map of the relation of mold temperature and moulded products glossiness.

Figure 35 illustrates heat insulation layer of the present invention and the metal level cross section with the die surface layer of micro concavo-convex interface driving fit.

Figure 36 is the partial cross section key diagram that illustrates with the state of Fresnel lens die injection mo(u)lding under common condition of molding in the past.

Figure 37 is the partial cross section figure of the Fresnel lens die that uses in the inventive method.

Figure 38 illustrates with the cross section of the delustring shape moulded products of the inventive method injection mo(u)lding with the cross section of the delustring shape moulded products of the mold injection molding of passing by.

Figure 39 illustrates the injection-molded item that uses in the present invention's explanation.

Figure 40 is the resin pressure time history plot that die surface was subjected to when injection mo(u)lding was shown.

Figure 41 illustrates the key diagram that the synthetic resin that is injection molding is filled into the typicalness at die surface micro concavo-convex position.

Figure 42 illustrates the sectional view that makes moulded products forming mould of the present invention.

Figure 43 illustrates each operation of die surface being carried out etch processes.

Figure 44 illustrates each operation of die surface being carried out multistage etch processes.

Figure 45 represents die surface is carried out each operation of multistage etch processes.

Figure 46 is the curve map that the concave-convex surface pattern of moulded products among the embodiment 10 is shown.

Figure 47 is the curve map that the concave-convex surface pattern of mould and moulded products in the comparative example 9 is shown.

The preferred plan that carries out an invention

The synthetic resin that can adopt method of forming moulding of the present invention is the thermoplastic resin that can be used for general injection mo(u)lding or blow molding, is methacrylic resins such as phenylethylene resin series such as polyolefin such as polyethylene, polypropylene, polystyrene, SAN, polystyrene rubber reinforcement, styrene-methylmethacrylate copolymer, ABS resin, polymethyl methacrylate, copolymer of methyl methacrylatestyrene, polyamide, polyester, Merlon, vinyl chloride resin etc.

The resin that is particularly suitable for forming method of the present invention is selected from non-crystalline resins such as methacrylate resin, Merlon such as phenylethylene resin series such as polystyrene, polystyrene rubber reinforcement, SAN, ABS resin, styrene-methylmethacrylate copolymer, polymethyl methacrylate, rubber enhancing polymethyl methacrylate, and the resin that wherein also is added with various packing materials.

The present invention especially preferably uses the various synthetic resin that are added with inorganic filling materials such as powder such as fibers such as glass fibre, carbon fiber, whisker, calcium carbonate, titanium oxide, talcum by 5～65 weight % content.If will contain the synthetic resin injection mo(u)lding of the inorganic filling materials such as glass fibre, whisker of 5～65 weight % with heat insulation layer lining mould, then die surface is easy to be scratched by inorganic filling material.Especially, if the inorganic filling material that adds surpasses 20 weight %, then heat insulation layer easily is scratched.If the packing material that adds is equal to or higher than 30 weight %, then die surface is easily significantly scratched.Among the present invention, make the metal level that exists hardness or higher and suitable thickness identical on the die surface, can prevent from thus to scratch with inorganic filling material.And general release property with the heat insulation layer with polar group such as polyamide, resin that acrylonitrile content is high is poor, under this occasion, makes on this heat insulation layer surface to exist metal level can improve release property.

The resin that is suitable for most forming method of the present invention is that to be added with 1～10 weight % rubber, glass transition temperature be 80～120 ℃ polystyrene rubber reinforcement.

Forming method of the present invention can be used for synthetic resin injection-molded items such as the shell of the general light current machine of moulding, electronic instrument, office equipment etc., various automobile component, various commodity, various industrial parts.Be particularly preferred for the injection mo(u)lding of many cast gates, easily produce electronic instrument, the electric machine of many weld bonds, shell of office equipment etc.And, also can be used for obtaining injection-molded items such as lens, high permeability, high scatter plate such as delustring shape moulded products, floral designs moulded products, the biconvex lens of using the lucite moulding, Fresnel lens.Can obtain various moulded products well with method of the present invention, good, the significant weld bond of the repeatability of the die surface of these moulded products reduces, and the repeatability of the repeatability of the sharp edges of die surface and die surface micro concavo-convex is also good.When these injection-molded items adopt general injection molding method moulding, effect is remarkable under the occasion that synthetic resin is used in combination the pressure of die cavity wall low pressure injection formaing low and/or that synthetic resin flowing velocity in mould is slow during particularly with moulding such as for example gas assistant injection molding, liquid aid injection molding, oligomer aid injection molding, injection compression moldings, can be used for the present invention well.

And method of the present invention can be used for the various blow-molded articles of moulding requirement outward appearance.

Metal system master mould described in the present invention comprises iron or is the steel, aluminium of main component with iron or is the metal die that kirsite, the beryllium-copper alloy etc. such as alloy, ZAS of main component are generally used for molding synthetic resin with aluminium.The mould that especially preferably uses steel such as S55C, S45C to make.Preferably carry out plating with the contacted die surface of heat insulation layer of these metal systems master mould with hard chromium or nickel etc.

The heat resistant polymer that preferably uses as heat insulation layer among the present invention, its softening temperature ratio is by the synthetic resin height of moulding, and glass transformation temperature is preferably more than 140 ℃, more preferably more than 160 ℃, most preferably more than 190 ℃, and/or its fusing point is preferred more than 200 ℃, more preferably more than 250 ℃.Particularly preferred polymer, its softening temperature ratio is by the forming temperature height of the synthetic resin of moulding.The thermal conductivity of heat resistant polymer is generally 0.0001～0.003 card/cps ℃, and is more much smaller than metal.And the preferred elongation at break of this heat resistant polymer is more than 4%, and is preferred more than 5%, more preferably the polymer with toughness more than 10%.The assay method of elongation at break is undertaken by ASTM D638 standard, and the draw speed during mensuration is the 5mm/ branch.

Preferably use the heat resistant polymer that has aromatic ring on the main chain as heat insulation layer among the present invention, for example, can use the various amorphism heat resistant polymers that are dissolved in organic solvent and various polyimides etc.The amorphism heat resistant polymer is polysulfones, polyether sulfone etc.In these amorphism heat resistant polymers, add packing materials such as carbon fiber or various inorganic filling materials, can reduce thermal coefficient of expansion, can be used as heat insulation layer of the present invention.In the various polyimides, preferably use straight chain polymer amount polyimides, partially crosslinked polyimides.The elongation at break of straight chain polymer amount polyimides is big, and tough, and durability is good, is preferred especially the use.Also comprise polyamidoimide, PEI in this straight chain polymer amount polyimides.

And, also can use thermal coefficient of expansion circlet epoxy resins solidfied material among the present invention, promptly, make the curing agent that thermal coefficient of expansion reduces and the epoxy resin cured product of epoxy resin combination, or the epoxy resin cured product etc. that adds various packing materials in right amount (followingly abbreviates epoxy resin cured product as epoxy resin.)。Generally speaking, the thermal coefficient of expansion of epoxy resin is big, and is big with the difference of the thermal coefficient of expansion of metal die.But, preferably use the epoxy resin of packing materials such as powder such as being added with the little glass of thermal coefficient of expansion, silica, talcum, clay, zirconium silicate, lithium metasilicate, calcium carbonate, aluminium oxide, mica in right amount or particle, glass fibre, whisker, carbon fiber as heat insulation layer of the present invention, reduce poor with the thermal coefficient of expansion of metal die.

And epoxy resin or packing material add in the epoxy resin, more preferably use add tough thermoplastic resin such as nylon, have rubber etc. obdurability various additives and have the composition epoxy resin of obdurability.Especially preferably use in the epoxy resin the good polymer alloy of obdurability that adds polyether sulfone or PEI and solidify.

In order to improve the closing force that waits the metal level that on heat insulation layer, forms through electroplating, preferably in the heat resistant polymer that forms heat insulation layer of the present invention, add micropowders such as titanium oxide, aluminium oxide, calcium carbonate.This micropowder can add in the whole heat insulation layer, also can only add the position, top layer to.If the addition of these micropowders is too much, then the thermal conductivity of heat insulation layer reduces, and is difficult to reach purpose of the present invention, generally adds micropowder by the scope of 1～30 weight %.

In injection mo(u)lding or the blow molding etc., in each forming process, be subjected to harsh cold cycling with the die surface that is contacted by the heating resin of moulding.Adopt technology in the past, wait the metal level that on the heat insulation layer surface, forms by electroplating, its thermal coefficient of expansion is generally less than the heat insulation layer that polymer constitutes, because the thermal expansion coefficient difference of heat insulation layer and metal level is bigger, during each moulding, it produces stress at the interface repeatedly, peels off on its interface.The difference of the thermal coefficient of expansion by making the main mould that contacts with heat insulation layer and/or metal level and the thermal coefficient of expansion of heat insulation layer reduces, and can reduce and cause the stress of peeling off.Among the present invention, the difference of the thermal coefficient of expansion of the main mould that contacts with heat insulation layer and/or the thermal coefficient of expansion of metal level and heat insulation layer preferably is lower than 4 * 10 ^-5/ ℃, more preferably less than 3 * 10 ^-5/ ℃.Usually, therefore the thermal coefficient of expansion of metal, preferably selects the little heat resistant polymer of thermal coefficient of expansion less than polymer.Thermal coefficient of expansion described herein is a linear expansion coefficient.The thermal coefficient of expansion of heat insulation layer is the linear expansion coefficient on the in-plane of heat insulation layer, adopt the method shown in the JISK7197-1991 to measure, represent with the mean value between 50 ℃ and 250 ℃, perhaps under the glass transition temperature of heat insulation layer is lower than 250 ℃ occasion, represent with the mean value between 50 ℃ and this glass transition temperature.That is, on level and smooth tabular metal, form heat insulation layer, then peel off this heat insulation layer, measure this heat insulation layer between 50 ℃ and 250 ℃ or the mean thermal expansion coefficients between 50 ℃ and the glass transition temperature.

Peeling off between heat insulation layer and the main mould or between heat insulation layer and the metal level, its reason are not only the difference of thermal coefficient of expansion.But the difference of thermal coefficient of expansion is great factor.The closing force of heat insulation layer and main mould and/or metal level is big, and the stretch modulus of heat insulation layer is little, and elongation at break is big, if the heat insulation layer of so-called rubber-like soft material is not peeled off even the difference of thermal coefficient of expansion more can not produce.But, be suitable for the material of heat insulation layer, promptly, satisfy hear resistance height, hardness big, easily by grinding the heat-insulating material that forms minute surface etc., it generally is the hear resistance hard resin that on the big main chain of modulus, has aromatic ring, in order to make this hear resistance hard resin layer driving fit on main mould and/or metal level and do not cause and peel off, the little synthetic resin of difference of preferred thermal coefficient of expansion.

Shown in the table 1 among the present invention the preferred main mould that uses with the metal level of metal, outermost layer lining with metal, heat insulation layer thermal coefficient of expansion with heat resistant polymer and general synthetic resin.

Table 1

	Material	Thermal coefficient of expansion
	Material	Thermal coefficient of expansion	Main mould and metal level	Steel	1.1 ×10 ^-5/℃
Aluminium	2.2 ″			Steel	1.1 ×10 ^-5/℃
Aluminium	2.2 ″	Aluminium alloy		2.4 ″
Copper	1.7 ″	Aluminium alloy		2.4 ″
Copper	1.7 ″	Brass		1.9 ″
Zinc	3.3 ″	Brass		1.9 ″
Zinc	3.3 ″	Kirsite (ZAS)		2.8 ″
Tin	2.0 ″	Kirsite (ZAS)		2.8 ″
Tin	2.0 ″	Chromium		0.8 ″
Nickel	1.3 ″	Chromium		0.8 ″
Nickel	1.3 ″	Heat insulation layer		Low-thermal-expansion type polyimides	0.4～3 ″
Common polyimides	3～6 ″			Low-thermal-expansion type polyimides	0.4～3 ″
Common polyimides	3～6 ″		Polybenzimidazoles	2.3 ″
Polyamidoimide	3～7 ″		Polybenzimidazoles	2.3 ″
Polyamidoimide	3～7 ″		Polyether sulfone	4～5.5 ″
Polysulfones	4～5.6 ″		Polyether sulfone	4～5.5 ″
Polysulfones	4～5.6 ″		PEI	4～5.6 ″
Synthetic resin	Acrylic resin		PEI	4～5.6 ″		6～9 ″
	Acrylic resin	Polystyrene resins	3～12 ″			6～9 ″
	Mylar	Polystyrene resins	3～12 ″	5～10 ″
	Mylar	Epoxy resin	6～10 ″	5～10 ″
	Nylon resin	Epoxy resin	6～10 ″	8～13 ″
	Nylon resin	Polyvinyl resin	8～18 ″	8～13 ″

If the thermal coefficient of expansion of main mould and/or metal level increases, can use the big relatively heat insulation layer of thermal coefficient of expansion.As mold material, the most frequently used is steel, also can use kirsites such as aluminium alloy or ZAS recently.Among the present invention, thermal coefficient of expansion is approaching more good more, and main mould uses under the occasion of steel, preferably uses the minimum low-thermal-expansion type polyimides of thermal coefficient of expansion etc.

Be preferred for the structure (repetitive) and the glass transition temperature (Tg) of heat resistant polymer of the present invention shown in the table 2.

Table 2

But adopt injection mo(u)lding and blow molding one-shot forming ground to obtain complex-shaped moulded products, economically valuable in this regard.Preferable methods is with the be covered complex surface of this mould of heat resistant polymer, and in order to make its strong ground driving fit, be coated with heat resistant polymer solution and/or heat resistant polymer precursor solution thereon, then heating, form the heat insulation layer of heat resistant polymer, perhaps, make heat resistant polymer method such as vacuum evaporation polymerization on die surface.In order to form heat resistant polymer, preferably dissolve in the heat resistant polymer or the heat resistant polymer precursor of solvent by coating.The preferred method of using be solution coat with polyimides precursor polyamic acid to the die cavity wall, then be heating and curing, on the die cavity wall, form polyimides.The reaction equation that polyamic acid forms polyimides below is shown.

Polyimides precursor polyamic acid solution is applied on the die cavity wall, then be heating and curing, form polyimides, under this occasion, the temperature that is heating and curing and/or be heating and curing atmosphere gas difference, the glass transition temperature of polyimides or thermal coefficient of expansion difference.Usually, the temperature that is heating and curing is high more, and glass transition temperature is high more, and thermal coefficient of expansion is more little.Generally more than 250 ℃, polyamic acid almost 100% imidizate forms polyimides, thinks that the molecular behavior that changes into behind the polyimides is influential to thermal coefficient of expansion.

Heat insulation layer of the present invention and main mould and/or heat insulation layer and metal level are that driving fit.Closing force is the bigger the better.Described in the present invention and heat insulation layer main mould driving fit or with the metal level of heat insulation layer driving fit, can not cause because of the molding synthetic resin more than 10,000 times cold and heat succeed each other to produce peeled off.More than the preferred 0.3kg/10mm of closing force under 23 ℃ is wide, more preferably 0.5kg/10mm wide more than, most preferably 0.7kg/10mm wide more than.This is that the metal level of driving fit or metal level and heat insulation layer are cut into 10mm is wide, with the rectangular direction in composition surface on the speed of dividing with the 20mm/ peeling force when stretching.This peeling force deviation that appearance is very big along with mensuration place, mensuration number of times etc. are different, importantly minimum of a value is big, preferred stable big closing force.In order to improve the closing force of main mould and heat insulation layer, can implement aptly to make main die surface form fine concavo-convex, on main die surface, carry out various plating or carry out operations such as primary coat processing.Preferred embodiment as primary coat is handled contains CO group, SO ₂The polyimides that group is many is easy to driving fit to the metal surface, and the polyimide coating that these adaptations are good can use the method for the common polyimides of lining thereon as priming coat.

The closing force of heat insulation layer and metal level is the bigger the better, and the two is preferably with the driving fit of micro concavo-convex interface.That is, preferably filling up generation anchor effect mutually by heat insulation layer and metal level on its interface increases closing force.Heat insulation layer and metal level micro concavo-convex at the interface, its size is concavo-convex about 0.5～10 μ m for filling up distance mutually, the preferred concavo-convex intricately of part is filled up and is produced the concavo-convex of anchor effect.The micro concavo-convex degree is to measure with the cross section of the interface locations of microscopic examination heat insulation layer and metal level.Preferred micro concavo-convex degree is in datum length is 80 μ m, the interface of metal level and heat insulation layer concavo-convex is 0.5～10 μ m from the difference of the mean value of the summit absolute altitude of 5 projectioies of a projection to the and the mean value of the lowest point absolute altitude that is recessed into the 5th depression from.Because concavo-convex intricately described herein is filled up the shape that produces the anchor effect mutually, rather than simple concavo-convex, so absolute altitude is selected each the darkest concavo-convex position.

The maximum strong point of injection mo(u)lding or blow molding is to make complex-shaped goods one-shot forming, so mold cavity is generally complicated shape.But, it is extremely difficult that the material that will be covered on this complex-shaped mold cavity surface is coated with into mirror-like, therefore the best way is that coated coating is carried out surface grinding, or, carry out surface grinding then and be processed into mirror-like with various work mechanism cutting coating layers such as CNC milling machines.

Among the present invention, the gross thickness of heat insulation layer can be selected in the scope that satisfies the integrated value of appointment of the present invention, mold surface temperature variation, can select in the extremely narrow scope of 0.1mm～0.5mm.In the injection mo(u)lding more preferably 0.1mm～0.4mm, be preferably 0.12mm～0.3mm especially, in the blow molding, be preferably 0.2mm～0.5mm, more preferably 0.3mm～0.5mm.The thin heat insulation layer that is lower than 0.1mm can not get the effect that outward appearance substantially improves.Heat insulation layer thickness is blocked up, and then the necessary cool time in the mould is long, unfavorable economically during moulding.

In the moulding of thermoplastic resin, mold temperature and molding cycle time are closely related.That is, during moulding, represent with following formula on the relational theory of the necessary cool time (θ) in mold temperature (Td) and the mould.

θ＝-(D ²/2πα)·ln[(π/4){(Tx-Td)/(Tc-Td)}]

θ: cool time (second)

D: the thickest of moulded products (centimetre)

Tc: the heating resin temperature during moulding (℃)

Tx: the softening temperature of moulded products (℃)

α: the thermal diffusivity of resin

Td: mold temperature (℃)

Cool time (θ), 2 powers with moulded products wall thickness (D) were directly proportional, and were the function of (Tx-Td)/(Tc-Td).

The heat insulation layer that is covered on main mould increases with the moulded products wall thickness, prolong have identical effect cool time, and on the other hand, mold temperature reduces, and then shortens cool time.The thin thickness of heat insulation layer can improve outward appearance, and this point is both economical on the time at molding cycle.Among the present invention, preferred especially with the heat insulation layer thickness setting in above-mentioned close limit, can satisfy outward appearance so well and improve and the molding cycle time.

In the known document of lining heat insulation layer and metal level, most heat insulation layer thickness is big on the mould.If heat insulation layer thickness is big, the repeatability of die surface is good, but is unfavorable for molding cycle time that productivity, economy are had a significant impact.

With concrete data heat insulation layer thickness and molding cycle time relation are described.Use the two kind heat insulation layer lining moulds of heat insulation layer as 0.6mm and 0.2mm, compare thick necessary cool time of moulded products of injection mo(u)lding 2mm, under this occasion, the synthetic resin of injection mo(u)lding and the thermal conductivity of heat-insulating material generally are roughly peer-level, so the ratio of the necessary cool time of the ratio of the necessary cool time in the mould moulded products moulding thick with making the thick and 2.2mm of 2.6mm is roughly the same.Moulding 2.6mm is thick and the ratio of the necessary cool time that 2.2mm is thick, shown in following formula, is 2.6 ²/ 2.2 ²=1.4.Differ from 1.4 times necessary cool time, under the occasion of industrial shaping synthetic resin, considers that from the economy aspect then difference is very big.

The mould that uses among the present invention, the preferable alloy that is used for the metal level that is covered on its heat insulation layer surface is generally and can be used for electroplated metal, is chromium, nickel, copper etc. more than a kind or a kind.What preferably use is chemical nickel plating, electrolytic ni plating, electroless copper, electrolytic copper plating, electrolysis chromium plating etc.Metal level is overlayed on the surface of heat insulation layer.Heat insulation layer and metal level must be driving fits, and its closing force is preferably more than the 0.3kg/10mm, more preferably more than the 0.5kg/10mm, most preferably are more than the 0.7kg/10mm.The preferred especially chemical deposit of layer that directly contacts with heat insulation layer.

The surface of metal level can be decorative pattern shapes such as the delustring shape on mirror-like, micro concavo-convex surface, lenticular, leather patterns or the wood grain of fine lenticular convex-concave surface etc. any, can select as required.Being preferred for decorative pattern shape of the present invention is patterns such as leather patterns, wood grain, hair line.In order to make textured surface appear in one's mind out, preferably make a concavo-convex side of decorative pattern shape die surface be minute surface, the opposing party is a delustring face.Perhaps, make the concavo-convex suitably in small, broken bits of textured surface, make a concavo-convex side for minute surface, the opposing party be the delustring shape, comprises also among the present invention that usefulness is added with the molding synthetic resin of flake aluminum etc., obtains the outward appearance of so-called metal tone.

Lenticular is fine Fresnel lens, fine tabular lens such as biconvex lens.In the fine lenticular mould, heat insulation layer is roughly certain thickness, and on the change metal level under the occasion of lenticular thickness, with the thickness of metal level thin-walled portion as the metal layer thickness described in the present invention, on the contrary, metal level is roughly certain thickness, and changes under the occasion of lenticular thickness on the heat insulation layer, with the thickness of heat insulation layer thin-walled portion as the heat insulation layer thickness described in the present invention.

The preferred thickness of heat insulation layer thickness and metal, along with the difference of any die surface of mirror-like, delustring shape, decorative pattern shape and difference, and, the difference along with the difference of injection mo(u)lding, any forming method of blow molding.In each forming method, preferred heat insulation layer thickness and preferred metal layer thickness are shown specifically as follows.

Be shaped to injection molding method under the occasion of mirror-like or delustring shape moulded products, preferably, heat insulation layer thickness is 0.1mm～0.4mm, metal layer thickness is below 1/3 of heat insulation layer thickness, and be 0.001～0.07mm, more preferably, heat insulation layer thickness is 0.12mm～0.3mm, metal layer thickness is 1/100～1/5 of a heat insulation layer thickness, and is 0.002～0.06mm.

Be shaped to injection molding method under the occasion of decorative pattern shape moulded products, preferably, heat insulation layer thickness is 0.1mm～0.4mm, and the thickness of metal level protuberance is below 1/3 of heat insulation layer thickness, and is 0.01～0.07mm, decorative pattern shape concave depth is 0.005～0.06mm, more preferably, heat insulation layer thickness is 0.12mm～0.3mm, and the thickness of metal level protuberance is below 1/5 of heat insulation layer thickness, and be 0.01～0.06mm, decorative pattern shape concave depth is 0.005～0.04mm.Concave depth is excessive, and then the die surface repeatability of recess and protuberance produces very big difference, influences the molding gradient of moulded products.Recess depths is too small, and then the effect of decorative pattern shape reduces.

Be shaped to blow molding method under the occasion of mirror-like or delustring shape moulded products, preferably, heat insulation layer thickness is 0.2mm～0.5mm, metal layer thickness is below 1/3 of heat insulation layer thickness, and be 0.002～0.1mm, more preferably, heat insulation layer thickness is 0.3mm～0.5mm, metal layer thickness is 1/100～1/5 of a heat insulation layer thickness, and is 0.004～0.06mm.

Be shaped to blow molding method under the occasion of decorative pattern shape moulded products, preferably, heat insulation layer thickness is 0.2mm～0.5mm, and the thickness of metal level protuberance is below 1/3 of heat insulation layer thickness, and is 0.01～0.1mm, decorative pattern shape concave depth is 0.005～0.09mm, more preferably, heat insulation layer thickness is 0.3mm～0.5mm, and the thickness of metal level protuberance is 1/100～1/5 of heat insulation layer thickness, and be 0.01～0.08mm, decorative pattern shape concave depth is 0.005～0.07mm.

Among the present invention, layer on surface of metal has under the concavo-convex occasion of decorative pattern shape, why with the metal thickness at the heavy wall position (being generally the protuberance thickness of metal level) of metal level metal layer thickness as the lining of the heat insulation layer in the forming method of the present invention mould, be for the die surface repeatability that makes protuberance is good, the minimizings such as significant weld bond of moulded products integral body.

Metal level is preferably homogeneous thickness, and the deviation of thickness preferably is lower than ± and 20%, more preferably less than ± 10%.Layer on surface of metal is under the concavo-convex occasion of decorative pattern shape, and the metal level of protuberance or the metal level of recess are preferably homogeneous thickness respectively, thickness deviation separately preferably is lower than ± and 20%, more preferably less than ± 10%.The deviation of metal layer thickness is big, the big part of metal layer thickness then, and its die surface repeatability is poor, and the good part of die surface repeatability is easy to appear on the surface of same moulded products with the part of difference.

The present invention relates to make the die surface repeatability and all very desirable forming method of molding cycle time of moulded products, but, preferably main mold temperature is set in lower temperature and carries out moulding in order to keep moulding short cycle time.Among the present invention, preferably main mold temperature is set in 15 ℃～100 ℃ and be lower than under the temperature of (synthetic resin softening temperature-20 ℃) and carry out moulding, more preferably, carries out moulding being lower than under the temperature of (synthetic resin softening temperature-30 ℃).Main mold temperature described herein is and the main mould of the heat insulation layer contact portion temperature when the moulding.Main mold temperature is equal to or higher than this temperature, then the necessary cool time in the mould elongated, so the molding cycle time is long, the shaping efficiency reduction.If main mold temperature is the high temperature above 100 ℃, the repeatability of die surface is fine certainly, but unfavorable to shaping efficiency.Main mold temperature is preferably 20 ℃～90 ℃, more preferably 25 ℃～80 ℃.Main mold temperature is lower than 15 ℃, and phenomenons such as dewfall then easily take place on the die surface.The softening temperature of problem on deformation appears in softening temperature described herein for moulded products integral body, contain under the occasion of additives such as glass fibre, different with softening temperature during for the softening temperature of the synthetic resin integral body that contains this additive (calculate following integrated value (second ℃)).

After selection was contacted 5 seconds with die surface by the synthetic resin of moulding among the present invention, mold surface temperature was reduced to the following condition of molding of synthetic resin softening temperature.In other words, contact within 5 seconds with die surface at synthetic resin, if mold surface temperature is equal to or higher than the synthetic resin softening temperature, then the die surface repeatability is good, considers from molding cycle time viewpoint, and mold surface temperature is reduced.And, in the injection molding forming method of the present invention, preferred condition of molding is, after synthetic resin contacts 5 seconds with die surface, mold surface temperature is reduced to below (synthetic resin softening temperature-10 ℃), and more preferably mold surface temperature is reduced to below (synthetic resin softening temperature-20 ℃).This can be met by each layer thickness, resin temperature, the mold temperature of suitable selection heat insulation layer and metal level.The die surface repeatability of moulded products is to contact 5 seconds with die surface with interior problem at synthetic resin in the injection mo(u)lding, in the injection mo(u)lding of standard 3 seconds with the injection mo(u)lding of interior, standard in 2 seconds, mold surface temperature height within these several seconds only, if be equal to or higher than the synthetic resin softening temperature, then consider, after several seconds die surface is cooled off fast from molding cycle time viewpoint.Therefore, particularly preferred condition is among the present invention, and after synthetic resin contacted 2 seconds with die surface, mold surface temperature was reduced to below the synthetic resin softening temperature.Contact with die surface within about 20 seconds at synthetic resin, if mold surface temperature is equal to or higher than the synthetic resin softening temperature, then the die surface repeatability is fine certainly, but the molding cycle time is long, can not use economically.

With the surface of heat insulation layer coated metal system master mould, when injected heating resin contacted with this surface, die surface was subjected to the heat of resin and heats up.The thermal conductivity of heat insulation layer is more little, and heat insulation layer is thick more, and mold surface temperature is high more.

Forming method of the present invention uses a kind of like this heat insulation layer lining mould, on the die cavity wall that constitutes metal system master mold cavity, exist the heat insulation layer that forms by heat resistant polymer, exist metal level on the heat insulation layer with its driving fit, condition of molding is: by the heating synthetic resin of moulding with after die surface contacts, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the integrated value (Δ H) of the value of (mold surface temperature-synthetic resin softening temperature) is more than 2 seconds ℃, and/or, be equal to or higher than at mold surface temperature during (synthetic resin softening temperature-10 ℃), the integrated value (Δ h) of the value of { mold surface temperature-(synthetic resin softening temperature-10 ℃) } is more than 10 seconds ℃.Mold surface temperature is for contacting by the interface temperature of the heating synthetic resin of moulding, and mold surface temperature and resin surface temperature are about equally.Among the present invention, mold surface temperature has identical meaning with the resin surface temperature.When the synthetic resin of heating plasticization contacted with the mould of cooling, heat was seized by the big metal level of thermal capacitance, and in a single day mold surface temperature reduces, and was warmed up to immediately more than the synthetic resin softening temperature, and then reduced.We find, die surface be in the above time of synthetic resin softening temperature and than high how many these two factors of softening temperature during to moulding the repeatability of die surface influence very greatly, so far finish the present invention.Promptly, among the present invention, by the heating synthetic resin of moulding with after die surface contacts, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, integrated value (Δ H) is more than 2 seconds ℃, and/or integrated value (Δ h) is more than 10 seconds ℃, carries out moulding under this condition of molding, and then the die surface repeatability is good.This integrated value is equivalent to by this curve and the cingens area of synthetic resin softening temperature line in the mold surface temperature time history plot, perhaps is equivalent to the area that is surrounded by this curve and (synthetic resin softening temperature-10 ℃) line.

For injection mo(u)lding, preferred integrated value (Δ H) is 2 seconds ℃～50 seconds ℃, more preferably 5 seconds ℃～40 seconds ℃, is preferably 7 seconds ℃～40 seconds ℃ especially, most preferably 8 seconds ℃～40 seconds ℃.Preferred integrated value (Δ h) is 10 seconds ℃～100 seconds ℃, more preferably 12 seconds ℃～70 seconds ℃, is preferably 15 seconds ℃～70 seconds ℃ especially, most preferably 20 seconds ℃～70 seconds ℃.

Blow molding is compared with injection mo(u)lding, because synthetic resin is low to the pressure of die surface, and contact the back with die surface long to the time of pressurization, so the integrated value of necessity is big.For blow molding, preferred integrated value (Δ H) is more than 10 seconds ℃, and more preferably more than 20 seconds ℃, preferred integrated value (Δ h) is more than 20 seconds ℃, more preferably more than 30 seconds ℃.

At layer on surface of metal is to have under the occasion of ridge design shape, adopts the integrated value of the big part of metal layer thickness (general protuberance is thick).

The upper limit of integrated value considers that from viewpoints such as molding cycle times integrated value in the injection mo(u)lding (Δ H) is preferred below 50 seconds ℃, and more preferably below 40 seconds ℃, on the other hand, integrated value (Δ h) is preferred below 100 seconds ℃, more preferably below 70 seconds ℃.

In the blow molding, integrated value (Δ H) is preferred below 200 seconds ℃, and more preferably below 100 seconds ℃, integrated value (Δ h) is preferred below 400 seconds ℃, more preferably below 300 seconds ℃.Among the present invention, consider, preferably in the scope that can obtain practical die surface repeatability, select little condition of molding and the mould structure of integrated value from the viewpoint of molding cycle time.

The synthetic resin softening temperature that adopts when calculating integral value (Δ H) and integrated value (Δ h) is the temperature that synthetic resin deforms easily.For the additive that adds in the synthetic resin for easily deform when the moulding as rubber etc., be dissolved in the material in organic matter or the synthetic resin, under this occasion, be the softening temperature of the synthetic resin integral body that contains these additives.On the other hand, for the synthetic resin that is added with those packing materials that in synthetic resin, do not deform when the moulding such as inorganic powders such as fibers such as glass fibre, whisker, carbon fiber, calcium carbonate, be the softening temperature of the substrate synthetic resin of removing these inorganic filling materials.Make the synthetic resin that contains the packing material that when moulding, in synthetic resin, does not deform carry out moulding, under this occasion, in order to make the die surface repeatability good, preferred moulding product surface lining substrate synthetic resin, preferred moulding product surface does not expose the state of inorganic filling material basically.Therefore, when moulding, when resin contacted with die surface, the gap that substrate synthetic resin must pass the inorganic filling material that is present in the moulded products near surface arrived die surface, and the flowability of base resin is directly connected to the die surface repeatability.Therefore, the synthetic resin of the packing material that does not deform in synthetic resin when being added with moulding, the softening temperature when calculating its integrated value is represented (softening temperature that uses when setting mold temperature problem on deformation occurs, contains the softening temperature of the resin integral body of additive as moulded products integral body) with the base resin softening temperature.Softening temperature concerning non-crystalline resin with vicat softening temperature (ASTM D1525) expression, concerning the hard crystalline resin with heat distortion temperature (the ASTM D648 18.6kg/cm that loads ²) expression, concerning soft crystalline resin with heat distortion temperature (the ASTM D648 4.6kg/cm that loads ²) expression.Non-crystalline resin is for example polystyrene, polystyrene rubber reinforcement, Merlon etc., and the hard crystalline resin is for example polyformaldehyde, nylon 6, nylon 66 etc., and soft crystalline resin is for example various polyethylene, polypropylene etc.

And among the present invention, the maximum temperature that heats up immediately after the mold surface temperature of rising once reduces preferably is equal to or higher than (synthetic resin softening temperature+20 ℃).

Among the present invention, in order to be more than 2 seconds ℃ at integrated value (Δ H), and/or integrated value (Δ h) is the condition of molding compacted under more than 10 seconds ℃, selects the conditions of molding such as kind, resin temperature or mold temperature of heat insulation layer and metal layer thickness, synthetic resin.

The objective of the invention is to make good and maintenance moulding short the two compatibility cycle time of die surface repeatability.Therefore, if seek out the good necessary mold surface temperature of die surface repeatability is changed, promptly seek out and make the good necessary integrated value of die surface repeatability (Δ H), integrated value (Δ h), making the quick reduction of mold surface temperature after this is necessary to shortening the molding cycle time.And integrated value (Δ H), integrated value (Δ h) must be equal to or higher than and can obtain the necessary value of die surface repeatability, then there is no need but be equal to or higher than this value significantly, preferably the numerical value of the minimum of approaching necessity.

In order to reach these purposes, preferred condition of molding is among the present invention, after being contacted 5 seconds with die surface by the synthetic resin of moulding, mold surface temperature be reduced to the synthetic resin softening temperature following, preferably be reduced to (synthetic resin softening temperature-10 ℃) following, more preferably be reduced to below (synthetic resin softening temperature-20 ℃).This is the restriction item that does not make the increase of molding cycle time.More preferably, main mold temperature is set in 15 ℃～100 ℃, and be lower than the temperature of (synthetic resin softening temperature-20 ℃), preferred settings is at 20 ℃～90 ℃, and be lower than the temperature of (synthetic resin softening temperature-20 ℃), preferably set 25 ℃～80 especially, and be lower than the temperature of (synthetic resin softening temperature-30 ℃), making heat insulation layer thickness is 0.1mm～0.5mm, stipulates the scope of integrated value (Δ H) and integrated value (Δ h) under above condition.

During injection mo(u)lding or during blow molding, the variation of mold surface temperature can be calculated from synthetic resin, main mould, heat insulation layer temperature, specific heat, thermal conductivity, density etc.For example, use ABAQUS (U.S. Harbbit, Karlson ﹠amp; The software of Sorensen company) and ADINA and ADINAT (software of Massachusetts college of engineering exploitation) etc., can adopt the plain method of nonlinear finite element to come out with non-constant heat conduction analytical Calculation.The value that integrated value of the present invention (Δ H) and integrated value (Δ h) go out for the change calculations by mold surface temperature.This calculated value is not considered the shearing heating of synthetic resin in the injection mo(u)lding and the interfacial film thermal conductivity factor between each layer.Mold surface temperature shown in the figure of the present invention changes the numerical value that calculates with ABAQUS under these conditions.

Metal level of the present invention can adopt the whole bag of tricks to be covered, and preferably adopts plating.Plating described herein is chemical plating (electroless plating) and electroplates.The following several operations of preferred experience are carried out plating among the present invention.That is, at first make the heat insulation layer surface form micro concavo-convex, then carry out chemical plating.

Preliminary treatment → chemical attack (carrying out chemical etching with the strong acid solution of strong oxidizer etc.: make the surface form suitable micro concavo-convex shape) → neutralization → sensitiveness processing (make the synthetic resin surface be adsorbed with the slaine of reducing power, make it activation effect) → activation processing (will have the noble metals such as platinum of catalytic action to be deposited to resin surface) → chemical plating (chemical nickel plating, electroless copper etc.) → plating (electrolytic ni plating, electrolytic copper plating, electrolysis chromium plating etc.).

In order to increase the closing force of heat insulation layer and coating, most preferably the method for Shi Yonging is, in the outermost heat-insulating material of formation at least of heat insulation layer, be added into micronized etching auxiliary agents such as organic micropowder such as inorganic matters such as calcium carbonate, silica, titanium oxide, brium carbonate, barium sulfate, aluminium oxide, various polymer, adopt this powder of chemical attack stripping, make the surface form the micro concavo-convex shape of appropriateness, carry out plating then.Micronized etching auxiliary agent preferably adds in heat-insulating material about 1～30 weight %.

Below describe in detail and be preferred for chemical nickel plating of the present invention.

Chemical plating is metal ion to be reduced into metal and the method separated out with reducing agent.Usually, chemical plating must meet the following conditions.It is stable under the state of adjusting plating bath to enumerate (1) reducing agent, and selfdecomposition does not take place.(2) precipitation does not appear in the product after the reduction reaction.(3) can pass through pH, solution temperature control speed of separating out, etc.In the chemical nickel plating, use sodium hypophosphite, hydroxide boric acid etc. in the reducing agent, especially preferably use sodium hypophosphite.In order to satisfy above-mentioned condition, in chemical plating fluid, add principal component (slaine, reducing agent) auxiliary element (pH conditioning agent, buffer, promoter, stabilizing agent etc.) in addition.Sodium hypophosphite as reducing agent can use simultaneously with various auxiliary elements, and the result contains phosphorus in the nickel coating of formation.

Contain phosphorus 1 weight %～5 weight % among the present invention with in the preferred chemical Ni-plating layer of heat insulation layer driving fit, more preferably contain 2 weight %～5 weight %.The thickness of this chemical Ni-plating layer is for generally to be called the such thin layer of priming coat, and preferred 0.1～5 μ m is more preferably about 0.2～2 μ m.Among the present invention in the used heat insulation layer lining mould, must make the driving fit securely of chemical Ni-plating layer and heat insulation layer, therefore, at the initial stage of chemical nickel plating, most preferably by reducing the temperature of plating bath, regulate the pH value and slow down plating speed, generate the plating particle of small particle diameter, make the plating particle go deep into the inside of the micro concavo-convex on heat insulation layer surface.Form after the certain thickness coating, improve plating speed, carry out high efficiency plating.Its result contains phosphorus 1 weight %～5 weight % in the chemical nickel coating that contacts with heat insulation layer of formation, can form chemical nickel coating, electrolytic copper plating layer of electrolytic nickel coating, electrolysis chrome plating, phosphorous 5～14 weight % etc. on this coating.Directly carry out the chemical nickel plating of high phosphorus content on the heat insulation layer surface, during the above chemical nickel plating of particularly phosphorous 8 weight %, the general nickel particles that generates becomes big, and the closing force of coating reduces.

Below explain in the present invention as the lip-deep metal-plated of the most suitable polyimide layer of heat insulation layer.Metal-plated on the polyimide surface is at first carried out polyimide surface and is handled.Shown in No. 4,775,449, this method such as U.S. Patent No. and 4,842, No. 946 specifications of U.S. Patent No. etc., generally with processing polyimide surfaces such as alkali.That is, a little less than the alkalescence of polyimides, make surface active.But,, must have the sufficient dhering strength that only tolerates this impact that colds and heat succeed each other acutely because the metal level on heat insulation layer surface can be subjected to the violent impact that colds and heat succeed each other in molding synthetic resin.We have carried out various discussions, found that, lining is added with the polyimides of micronized etching auxiliary agents such as calcium carbonate, titanium oxide, aluminium oxide on the polyimides top layer, its surface of strong acid solution etching with strong oxidizer, micropowder and part polyimides such as the calcium carbonate that exists in the stripping top layer, titanium oxide, aluminium oxide, make the polyimides laminar surface form the micro concavo-convex shape of appropriateness, then, through neutralization, sensitiveness processing, the active processing, carry out chemical nickel plating, this method is the preferred method of using among the present invention.Micropowder also can use organic matters such as crosslinked rubber micropowder, slightly solubility micro polymer powder.

Below illustrate in greater detail and be preferred for plating instantiation of the present invention.Most preferred method is among the present invention, with average grain diameter is micropowder such as fine calcium carbonate, titanium oxide, aluminium oxide about 0.001～5 μ m, add in the polyimides by 1～30 weight %, preferred 5～25 weight %, fully mixing with polyimides, with the polyimides that mixes as outermost layer.Under this occasion, whole polyimide layer can be the polyimides that mixes, and also can have only outermost layer is the polyimides that mixes.These micropowders easily condense, and with polyimides precursor solution is fully mixing it are disperseed fully, and it is applied on the die surface, and heating makes it form polyimides.Then, with the strong acid solution that contains chromic acid, sulfuric acid, phosphoric acid etc. this polyimide surface is carried out etch processes, the micropowder and the part polyimides that are in the top layer are dissolved out, make polyimide surface form the micro concavo-convex of appropriateness, then through neutralization, sensitiveness handle, the active processing, sodium hypophosphite etc. is carried out chemical nickel plating as reducing agent.Chemical nickel plating carries out on low speed ground under low temperature, weakly alkaline state, makes the nickel particles of generation little, and nickel plating is carried out in the inside that makes nickel particles be deep into polyimides laminar surface micro concavo-convex equably, improves closing force thus significantly.

Usually, under acid state, improve temperature and can carry out chemical nickel plating expeditiously.As reducing agent, under the weak base state, with low temperature, when low speed ground carries out chemical nickel plating, the phosphorus content in the nickel coating is 1 weight %～5 weight % with sodium hypophosphite.The preferred group of the chemical nickel coating that contacts with heat insulation layer of the present invention becomes the phosphorus that contains 1 weight～5 weight %.

It is to carry out with the temperature lower than the chemical nickel plating that generally carries out, lower speed that low temperature, low speed ground carry out the chemical nickel plating described in the present invention, preferred 5 ℃～50 ℃, more preferably 10 ℃～40 ℃ temperature, and the speed of preferred time per unit is 0.1 μ m～10 μ m.

With can attach various electrodeposited coatings on the chemical nickel plating thin layer of the firm driving fit of heat insulation layer.The preferred instantiation that also can attach on this chemical nickel plating thin layer below is shown.

(1) chemical nickel plating (phosphorous 5～18 weight %)

(2) electrolysis chromium plating (hard chromium plating etc.)

(3) electrolytic ni plating (gloss nickel plating, semi-glossy nickel plating, matt nickel plating etc.)

(4) electroless copper

(5) electrolytic copper plating is preferably selected lining more than at least 1 layer or 2 layers from these coating.For example can preferably adopt and on the chemical nickel plating thin layer, carry out electrolytic copper plating and/or electroless copper, carry out the nickel plating more thereon and improve the coating closing force.

Hard on the coating outermost layer, the difficult nickel coating that scratches or hard chrome plating etc. are preferably more than the 0.5 μ m, more preferably 1～50 μ m, preferred especially 2～30 μ m.

In the synthetic resin of moulding, inorganic filling materials such as glass fibre, whisker, calcium carbonate add under the occasion of 5～65 weight %, more preferably add under a large amount of occasion of 20 weight %～65 weight %, especially preferably add under the occasion of 30～50 weight % inorganic filling materials, the hardness of die surface outermost metal layer preferably with synthetic resin in the hardness of inorganic filling material be equal extent, perhaps be equal to or higher than the hardness of inorganic filling material.This hardness is relative, is the two to be rubbed mutually and the difficult the sort of hardness that scratches metal level.Under glass fibre and the occasion that the hard chrome plating is compared, useable glass fiber friction hard chrome plating comes comparison.The hardness of object is difficult to directly compare with numerical value along with the difference of material kind, compares with Vickers hardness (HV) among the present invention.Vickers hardness (HV) be will have the diamond pyramid of 136 degree drift angles as notcher, represent a kind of method of hardness with the ratio of the surface area of the indenture of loading and generation, unit is with kg/mm ²Expression.Express the Vickers hardness (HV) of representational plating and glass down.

Table 3

Material	Plating bath and other	Additive	Hardness (HV)
Material	Plating bath and other	Additive	Hardness (HV)	Electrolytic ni plating	The sulfamic acid salt bath	Do not have	200～550
The perchlorinate thing is bathed	Do not have	230～300			The sulfamic acid salt bath	Do not have	200～550
The perchlorinate thing is bathed	Do not have	230～300	Watts is bathed		Do not have	100～250
Watts is bathed	The semi-glossy polishing material	400～500	Watts is bathed		Do not have	100～250
Watts is bathed	The semi-glossy polishing material	400～500	Watts is bathed		The gloss polishing material	500～600
Chemical nickel plating	P content	3% in the coating	Watts is bathed		The gloss polishing material	500～600	-	500～800
	P content	3% in the coating	P content 5～6% in the coating	-	500～800		-	500～800
	P content 8～9% in the coating	-	P content 5～6% in the coating	-	500～800	500～800
	P content 8～9% in the coating	-	B content 1% in the coating	-	800	500～800
	Coating is N ₁-W-P ternary system	-	B content 1% in the coating	-	800	600
	Coating is N ₁-W-P ternary system	-	Electrolysis chromium plating	Sa Jinteshi bathes	-	600	750～1000
Oxalic acid bath	-	1000～2000		Sa Jinteshi bathes	-		750～1000
Oxalic acid bath	-	1000～2000		Glass	-	-	400～650
Soda lime glass	-	-	530～580	Glass	-	-	400～650
Soda lime glass	-	-	530～580	Aluminium is for silicate glass	-	-	640
Quartz glass	-	-	780～800	Aluminium is for silicate glass	-	-	640
Quartz glass	-	-	780～800	E glass	-	-	640

The hardness of chemical nickel plating (electroless nickel plating), different along with the difference of phosphorus content, the difference along with the heat treated difference after the plating.Cause the variation of hardness to be recorded in ISO DIS 4527 grades by the heat treatment of nickel plating.

Used as the glass fibre that adds in the synthetic resin is E glass more, and near no alkaline glass, it consists of E glass, SiO in the glass that the electrical apparatus product of exploitation is used ₂: 52～56 weight %, Al ₂O ₃: 12～16 weight %, CaO:16～25 weight %, MgO:0～6 weight %, B ₂O ₃: 8～13 weight %, Na ₂O and/or K ₂O:0～3 weight %.Make under the occasion of the molding synthetic resin that contains this glass in a large number, the hardness of the outermost metal layer of mould is preferably identical with the hardness of this glass or be equal to or higher than glass hard (HRC65.

The hardness of the metal level described in the present invention is identical with the hardness of inorganic filling material in the synthetic resin or be equal to or higher than its hardness, be meant the value of the Vickers hardness of metal level greater than (Vickers hardness-100) of inorganic filling material in the synthetic resin, the Vickers hardness of preferred metal layers is greater than the Vickers hardness of inorganic filling material, and more preferably the Vickers hardness of metal level is greater than the value of (Vickers hardness+50) of inorganic filling material.

These coats of metal that the present invention preferably uses are with micro concavo-convex interface and heat insulation layer driving fit.Therefore, the interface of coating and heat insulation layer is in the state that coating and heat insulation layer enter mutually.Under this occasion, the metal layer thickness described in the present invention adopts metal to account for the thickness of 50 volume % with top, and heat insulation layer thickness adopts heat-insulating material to surpass the thickness of 50 volume % part.

Layer on surface of metal of the present invention can be mirror-like, delustring shape, decorative pattern shape, lenticular etc.

The layer on surface of metal that plating is formed forms the method for decorative pattern shape, can adopt the whole bag of tricks.The preferred etching method that uses.Most preferably use etching method.If the outermost metal of mould can then can be adopted the method identical with the etching method that makes common metal mould formation decorative pattern to form decorative pattern by the etchings such as acid solution of electrolytic ni plating, electrolytic copper plating, chemical nickel plating etc.That is, the preferred method of using is with ultraviolet curable resin layer on surface of metal decorative pattern shape ground to be covered, and then forms decorative pattern with the acid etching agent.Metal level is under the occasion of nickel coating, and the chemical nickel coating that phosphorus content is equal to or higher than 8 weight % is difficult to use acid etching, and phosphorus content is easily etched less than the chemical nickel coating of 8 weight %.

Plating and Surface Finishing, 79, No.3, P.29～33 phosphorus content and the acid resistance of chemical nickel coating shown in (1992) etc., phosphorus content is high more, and acid resistance is good more.In the table 1 of above-mentioned document, acid resistance was good when phosphorus content was 10～12 weight %, and is general when being 7～9 weight %, is 1～4 weight % time difference.In the state diagram of nickel-phosphorus alloy, phosphorus content be 0～4.5 weight % be the β phase, be 11～15 weight % be the γ phase, be 4.5～11 weight % be γ mutually and β mixture mutually.γ is the excellent corrosion resistance of acid relatively, and when the 8 weight % that are commonly referred to as high phosphorus content were above, corrosion resistance was big.

During electrolytic nickel is electroplated, form difference, the etching difference, the nickel coating that phosphorus content is high is difficult to use acid etching.The pattern depth that etching forms waits according to adjusting, the easy etched metal level of etching period and the combination that is difficult to etched metal level and to regulate.And, form after the decorative pattern preferred metal level and/or the big metal level of hardness that uses thin excellent corrosion resistance on the metal level outermost layer, chemical nickel coating that promptly phosphorus content is high or electrolysis hard chrome plating etc.

Make die surface formation Fresnel lens or lenticulated method can consider the whole bag of tricks, preferably make with the following method and wait.

The preferred method of using is: (a) the metal level cutting that plating is formed with work mechanism and/or grind to form lentiform method, (b) cuts into lenticular with work mechanism with heat insulation layer, on this lenticular surface, carry out plating, then again with work machine cut and/or grind this surperficial method, (c) uses preformed lens model, with electroforming processing method coated metal layer in its surface, peel off this metal level, make the thin metal layer of lens surface, it is attached to method on the heat insulation layer etc.With (a) and (c) mould made of method, the thickness of its heat insulation layer is certain substantially, and metal layer thickness changes along with the shape of lens, on the other hand, with the mould that (b) method is made, the thickness of its heat insulation layer changes along with the shape of lens, and metal layer thickness is certain substantially.Comprise this two classes mould among the present invention.Under the occasion of heat insulation layer thickness variation, with the heat insulation layer thickness of thin-walled portion as heat insulation layer thickness.

With the lens that heat insulation layer lining mould molding of the present invention comes out, can fully reproduce the acute angle portion of mold cavity, obtain good lens.That is, when going out to have the lens of mold cavity acute angle portion with mould molding in the past, synthetic resin can not enter into the acute angle position of mold cavity fully, in order to mold the good lens in abundant reproduction bight, must set high mold temperature and carry out moulding.If mold temperature improves, then has the shortcoming that the molding cycle time is long, productivity ratio reduces.Among the present invention the molding cycle time is limited to very small increase, can obtains fully to reproduce the good lens in bight.

Even the occasion at the scattering moulded products of the high scattered power that obtains to have micro concavo-convex shape surface also has same problem, the moulded products that fully reproduces the die surface micro concavo-convex is difficult to moulding with mould in the past.Can obtain not have branch with mould of the present invention and reproduce the concavo-convex high scattering moulded products of die surface, particularly be shaped to making transparent synthetic resin injection mo(u)lding highly see through, high scatter plate etc. is most preferred forming method.In recent years, the back of the body irradiation of liquid crystal indicator requires that the height of function admirable sees through, high scatter plate.That is, require that the height that total light penetration is big, the parallel rays transmitance is little sees through, high scatter plate.These height of past see through, the employed plate of high scatter plate is to disperse the refractive index micropowder different with this lucite of calcium carbonate, barium sulfate etc. in transparent resins such as methacrylic resin, thereby incident ray is disperseed.But these micropowders absorb incident raies, are difficult to obtain highly see through, high scatter plate.Use face parallel on the die surface few among the present invention with this die surface, promptly, form the mould of the present invention on concavo-convex sharp-pointed micro concavo-convex surface, adopt forming method shown in the present to make the moulded products on the micro concavo-convex surface of abundant this die surface of reproduction, acquisition can make the moulded products of incident light abundant scattering on the moulded products surface.Its result thinks, even the addition of the micropowder that adds in the synthetic resin is few, does not perhaps add, and can obtain also that the very little height of parallel rays transmitance sees through, high scatter plate.This moulded products be a kind ofly so highly see through, high scatter plate, by total light penetration T (%), the scattered beam transmitance D (%) of ASTM-D1003 mensuration, the pass of parallel rays transmitance P (%) be:

T＝D+P

This is one of preferred using method in the forming method of the present invention for P＜0.045T.

Other examples of the preferred using method of forming method of the present invention below are shown.The present invention also can be used to form the goods such as shell of delustring shape outward appearance such as the household electrical appliances, office equipment of weld bond well, that is to say that these moulded products require to have with above-mentioned height with high scattered power and see through, the antipodal effect of high scatter plate.Make this moulded products forming mould, preferably use heat insulation layer lining mould of the present invention, its layer on surface of metal or part metals laminar surface form delustring shape surface through multistage blasting treatment and/or multistage etch processes.Preferred mould is a hardness with die surface metal level less than its inboard metal level and/or etching greater than at least 2 layers of metal level of its inboard metal level, forms delustring shape surface through multistage blasting treatment and/or multistage etch processes.Especially, the etching speed that the preferred mould that uses is the die surface metal level is more than 2 times of its inboard metal level etching speed more preferably, and above-mentioned metal level forms delustring shape surface through multistage blasting treatment and/or multistage etch processes.The preferred mould with this delustring shape surface that uses below illustrates in greater detail its method for making.

The die surface that constitutes the common die die cavity of making over forms the method for delustring shape, and the main method that adopts is to make die surface coarse with general sand-blast.Form the delustring shape for the heat insulation layer rough surface that makes heat insulation layer lining mould, at first consider sand-blast.With the be covered heat insulation layer surface of mould or the metal level blasting treatment on heat insulation layer surface become the delustring shape of heat insulation layer, when carrying out injection mo(u)lding with polystyrene rubber reinforcement etc., although think that die surface is uniform delustring shape, but by the synthetic resin injection-molded item of moulding is not uniform delustring shape, and very easily by scuffings such as nails.That is to say, bad phenomenon significantly appears in the moulded products that forms, though do not had irregular weld bond depression, injection-molded item easily is scratched, and the end of the general part of moulded products and weld and/or general part and resin flows easily becomes uneven delustring face.Method provided by the invention can solve the intrinsic problem of using these heat insulation layers with delustring shape surface to be covered and to occur on the formed in mould moulded products.Promptly, the invention provides a kind of like this forming method, this method can reduce showy weld bond, forms uniform frosting, improve marresistance etc., and the molding cycle time can not prolong, mold economically the molding synthetic resin goods of excellent appearance significantly.

The metal level on heat insulation layer surface, the hardness of special preferred mold cavity side surface metal-layer is less than its inboard metal level and/or etching the metal level more than 2 layers of having greater than its inboard metal level.This metal level is more than under 2 layers the occasion, and the thickness of the surface metal-layer of mold cavity side is preferably more than 1/2 of metal level gross thickness.For the multistage blasting treatment of metal level is become the delustring shape, the Vickers hardness number of surface metal-layer is preferably less than the value of (Vickers hardness-50) of its inboard metal level.That is, preferably be prone to concavo-convex metal and form surface metal-layer with blasting treatment.The hardness of object is difficult to directly compare with numerical value along with the difference of material kind, compares with Vickers hardness (HV) among the present invention.Vickers hardness (HV) be will have the diamond pyramid of 136 degree drift angles as notcher, represent a kind of method of hardness with the ratio of the surface area of the indenture of loading and generation, unit is with kg/mm ²Expression.Blasting treatment described herein is to make the common die surface form the blasting treatment of delustring shape, inorganic particles such as the diamond dust of various particle diameters, different shape, glass are sprayed onto on the die surface with gas-pressurized, thereby make die surface form the delustring shape, multistage blasting treatment is that mutually different particles such as particle diameter, shape, material are carried out blasting treatment more than 2 times.Preferably will there be the blasting treatment of particle of corner angle and the combinations such as blasting treatment of spheroidal particle to carry out.Multistage blasting treatment of the present invention is to implement through more than 2 times preferred 3～6 different blasting treatments.Under this occasion, there is no need in 3～6 blasting treatments, to carry out diverse processing.For example, can repeat A processing and B and handle two kinds of operations.Adopt the one-level blasting treatment to be difficult to obtain the frosting of requirement of the present invention.The hardness of chemical nickel plating (electroless nickel plating) is different along with the difference of phosphorus content, the difference along with the heat treated difference after the plating.The variation of the hardness that the heat treatment of nickel plating forms is recorded in ISO DIS 4527 grades.

Multistage described in the present invention be etched to through more than 2 grades, preferred 3～10 grades, more preferably etch processes is carried out in 4～8 grades repetitive operation.Adopt the one-level etch processes to be difficult to obtain the frosting of requirement of the present invention.Adopt multistage etch processes to form under the occasion of delustring shape to layer on surface of metal, the etching speed of die surface metal level is preferably more than 2 times of its inboard metal level etching speed, more preferably more than 3 times, is preferably especially more than 5 times.

If the metal of metal level can then can be adopted with making the common metal mould and form the identical etching method of etching method of decorative pattern by general etching solution etching such as electrolytic ni plating, electrolytic copper plating, chemical nickel plating.That is, partly cover layer on surface of metal, then carry out etch processes with solution of ferrous chloride or acid solution with ultraviolet curable resin.Repeat this covering and etching operation, make surface metal-layer form the delustring shape.

Metal level is under the occasion of nickel coating, and the chemical nickel coating that phosphorus content is equal to or higher than 8 weight % is difficult to etched, and it is easily etched that phosphorus content is lower than the chemical nickel coating of 8 weight %.The high nickel of phosphorus content that the preferred corrosion resistance of inboard metal level of metal level of the present invention is good.The preferred phosphorus content of surface metal-layer is the nickel of 3 weight %～8 weight %.The etching of electrolytic ni plating is the difference along with the difference of forming also, the difference along with the difference of sulfur content or phosphorus content.The phosphorus content height, then corrosion resistance is good.

In multistage blasting treatment described in the present invention who is carried out and/or the multistage etch processes, comprise the processing of total more than 2 times with blasting treatment and etch processes and usefulness.Under this occasion, preferably add up to the processing more than 3 times.Most preferably adopt method with one or more levels blasting treatment and the combination of multistage etch processes.

With the good micro concavo-convex surface that the delustring face of synthetic resin injection-molded items such as this formed in mould polystyrene rubber reinforcement preferably has marresistance, pencil test is carried out with the pencil of the following hardness of 2B, the preferred following hardness of B in this surface does not have remarkable cut.Pencil test is pressed JISK 5401 and is measured.Significantly cut is the cut of with the naked eye recognizing easily.

Use heat insulation layer lining mould to carry out under the occasion of moulding, also do not forming on the die surface under the state of cured layer, may need to apply the synthetic resin that makes the die cavity wall and reproduce the necessary pressure of die surface.When the die surface of heat insulation layer lining mould was the delustring shape of micro concavo-convex shape, the synthetic resin that does not form cured layer fully flowed into the recess depths of die surface micro concavo-convex, fully reproduces die surface.The recess of die surface micro concavo-convex is that acute angle also can fully be reproduced.Its result, with the heat insulation layer formed in mould delustring shape moulded products that is covered, the protuberance of its surperficial micro concavo-convex is an acute angle, this moulded products is by contacts such as nails, then the acute angle position easy damaged of concave-convex surface and breakage.We find, use the heat insulation layer lining mould that carries out multistage etching and/or multistage sandblast of the present invention, the recess of the micro concavo-convex of mould outermost metal layer is the obtuse angle, and synthetic resin fully enters the recess depths of micro concavo-convex, obtains to have the moulded products of the very difficult convex-concave surface that scratches.Promptly, for the concave bottom of making the layer on surface of metal micro concavo-convex is the mould at obtuse angle, preferred multistage etching of employing and/or multistage sandblast form the delustring shape, and most preferably formation method and the heat insulation layer of the present invention lining die assembly with this delustring shape surface uses, and so far finishes the present invention.

Among the present invention, preferably use injection molding method or blow molding method.

In the injection mo(u)lding, according to the difference of injected synthetic resin temperature, main mold temperature, injection pressure, the flowing velocity of synthetic resin in mould etc., die surface repeatability difference.Method of the present invention is that effect is remarkable under 20～300mm/ occasion of second in the average flow velocity of synthetic resin in mould, therefore preferred the use.More preferably inject moulding well with the low speed of 30～200mm/ second.Flowing velocity is more little in the mould, and the die surface repeatability is generally poor more, and the present invention's effect when the general poor low speed injection mo(u)lding of die surface repeatability is remarkable, therefore especially preferably uses.Injection compression molding or gas assistant injection molding etc. are generally the low speed injection mo(u)lding.Average speed generally is to adopt die cavity cast gate to the resin flows of the end that flows to calculate apart from the ratio with the flowing time of synthetic resin in mould in the mould, also adopts this value among the present invention.The present invention's effect under the occasion of low speed injection is remarkable, but is not limited to the low speed injection mo(u)lding, also can be used for general high-pressure injection molding.

In the blow molding, contact with die surface according to the synthetic resin temperature that is blow molded, main mold temperature, blow molding pressure, from the parison that is blow molded and to begin time that fully is applied to blow molding pressure the moulded products inner surface etc., the repeatability difference of die surface.Condition of molding among the present invention contacts the time that begins fully to be applied to blow molding pressure the moulded products inner surface from the parison that is blow molded and is preferably 1～10 second with die surface, more preferably 2～8 seconds, be preferably 2～5 seconds especially.Especially, among the present invention, at synthetic resin with after die surface contacts, be equal to or higher than at mold surface temperature under the state of synthetic resin softening temperature, if increase blow molding pressure, then the repeatability of die surface is better, increases blow molding pressure particularly preferably within contacting 5 seconds.

Use description of drawings the present invention.

Fig. 1～Figure 27 illustrates the result who calculates according to variation of mold surface temperature etc.As mentioned above, the variation of mold surface temperature can be used softwares such as ABAQUS, adopts non-constant heat conduction to resolve and calculates.Below narrate computational methods in more detail.For the wall thickness of resin, the thickness of nickel dam and polyimide layer is quite little, therefore the heat conduction phenomenon can be regarded as one dimension heat conduction problem.Under the stable state, the governing equation formula is represented with following formula.

K (d ²T/dx ²)=0 herein, k is the thermal conductivity of material, T is a temperature, x is the position.

And heat flux is represented according to the following formula of Fourier's rule.

Q=-k (dT/dx) herein, q is a heat flux.Use finite element method (FEM), use the matrix notation simultaneous equations, then draw following formula by these formula.

[K] { T}={F} herein, [K] is the heat conduction matrix, and { T} is whole node temperature vector, and { F} is a thermal flux vector.{ F} then can solve simultaneous equations if known to heat conduction matrix [K], obtains node temperature with thermal flux vector.

Practical Calculation can adopt commercially available general structure elucidation software to calculate.Calculate with ABAQUS herein.During this calculated, the heat conduction influence in interface heat conduction between synthetic resin and the metal level and the main mould was minimum, ignores.

The thermal conductivity that the CAE that mold surface temperature changes when being used for moulding of the present invention calculates and the value of specific heat are used the value of listing in measured value and the various document.That is,, adopt the measured value of the polyimides that uses as heat insulation layer among the embodiment for polyimides.For polystyrene, thermal conductivity adopts H.Lobo and R.Newman: " SPE ANTEC ' 90 ", the p.862 middle value of reporting, than thermal recovery J.Brandrup, " polymer handbook " (JohnWiley that E.H.Immergut writes; The Sons distribution) value of record in.For polyformaldehyde, the value of putting down in writing in " high molecular thermal diffusivity specific heat capacity thermal conductivity data handbook 1994 " (strain) ユ-テス publication that employing this longevity of bridge is just showing.Thermal conductivitys etc. according to condition determinations such as temperature and pressures and difference is considered Temperature Influence among the present invention, but are not considered the influence of pressure under the mensuration of strictness." processing and forming " Vol.8 (2), 92 (1996), " SPE, ANTEC ' 90 ", p.862 (1990), " processing and forming ' 90 ", the thermal conductivity and the relation of measuring pressure of polymer have been reported in 139 (1990) etc., according to assay method and difference, because fuzzy, therefore use thermal conductivity under the atmospheric pressure etc.The density that adopts is respectively polystyrene 884kg/m ³, polyformaldehyde 1420kg/m ³, polyimides 1420kg/m ³Difference according to the kind of epoxy resin and curing agent thereof, the performance of epoxy resin has very big-difference, and, the occasion that additives such as general interpolation inorganic matter use is a lot, therefore, is called separately under the occasion of epoxy resin, adopt each value of the most general thermal conductivity, specific heat and density respectively, can directly use the value in " Machine Design brief guide " (the 3rd edition was put down into the distribution of the kind Co., Ltd. of ball 4 years).That is, the thermal conductivity of epoxy resin is that 0.3W/mk, specific heat are that 1.1J/gk, density are 1850kg/m ³, these numerical value of employing and temperature and pressure are irrelevant.Each value of pottery, nickel, steel is selected from " compile on chemical brief guide, basis " (ball is apt to Co., Ltd.) that Japanization association compiles.The thermal conductivity of pottery adopts 2.1W/ (mk), adopts 5700kg/m than thermal recovery 454J/ (kgK), density ³

And during the CAE that mold surface temperature of the present invention changes calculated, the resin when not considering moulding was sheared heating.The polystyrene rubber reinforcement that calculates with CAE shown in Figure 30 rises because of shearing the temperature that causes resin of generating heat when injection mo(u)lding, thereby expresses the Temperature Distribution in resin cross section.The CAE The conditions of calculation is, resin is STYRON 492 (the rubber enhancement mode polystyrene that rising sun chemical industry Co., Ltd produces), resin temperature is 240 ℃, mold temperature is 50 ℃, mould is a steel, mold cavity thickness is 2mm, and the mobile distance from side gate to the end that flows is 290mm, and the resin flows time of mold cavity is 0.4 second (injection speed is 725mm/ second) and 1.0 seconds (injection speed is 290mm/ second).After resin shown in Figure 30 is filled in the mold cavity, apart from the Temperature Distribution in the resin cross section at cast gate 25mm place and 145mm place.At injection speed is under the 725mm/ high speed injection occasion of second, and it is big to shear caloric value, and resin quick heating, injection speed are low more, and caloric value is few more, and injection speed is that 290mm/ generates heat during second less.The present invention especially preferably uses, injection speed is that the factor of shearing heating diminishes, and shears heating and disregards interior under 20～300mm/ low speed injection occasion of second.

The dependence of thermal conductivity of each resin that uses among the present invention shown in Figure 28 and Figure 29 (λ) and specific heat (Cp) and temperature adopts the thermal conductivity shown in these figure and the value of specific heat during CAE of the present invention calculates.

Be that 50 ℃, the temperature of polystyrene rubber reinforcement (representing with HIPS among the figure) are when carrying out injection mo(u)lding under 240 ℃ the condition in the temperature of steel master mould shown in Fig. 1, Fig. 2 and Fig. 3, the calculated value that near the Temperature Distribution the die surface changes.

The numeric representation of each curve contacts the time (second) of beginning among the figure with the die surface that is cooled from heated synthetic resin.Heated synthetic resin contacts with die surface, by cooling (Fig. 1) fast.When being covered main die surface with heat insulation layer, die surface is subjected to heating up from the heat of heated synthetic resin.As shown in the figure, during with 0.1mm and 0.3mm heat insulation layer (polyimides) lining die surface (Fig. 2 and Fig. 3), the surface temperature of the heat insulation layer that contacts with synthetic resin (polystyrene rubber reinforcement) rises a lot, and the speed that temperature reduces also reduces.

Fig. 4 illustrates the mould of heated synthetic resin (polystyrene rubber reinforcement) and lining all thickness polyimides (representing with PI among the figure) on the die surface of steel master mould when contacting, and mold surface temperature is (calculated value) over time.Along with the polyimide layer thickening that is covered on the die surface, the reduction of mold surface temperature is significantly slack-off.

Fig. 5 is illustrated under various resin temperatures and the mold temperature, and when synthetic resin (polystyrene rubber reinforcement) contacted with the mould of lining 0.2mm thick polyimide on the die surface of steel master mould, mold surface temperature is (calculated value) over time.Synthetic resin temperature and mold temperature reduce, and then mold surface temperature also reduces.

Fig. 6 is illustrated under various moulded products thickness and the mold temperature, and when synthetic resin (polystyrene rubber reinforcement) contacted with the mould of lining 0.2mm thick polyimide on the die surface of steel master mould, mold surface temperature is (calculated value) over time.

Fig. 7 illustrates use be covered polyimide layer, be covered in its surface behaviour's tool of nickel dam (representing with Ni among the figure) again on the die surface of steel master mould, as a comparison, use the mould of the polyimide layer that only is covered, main mold temperature is set at 50 ℃, at the polystyrene rubber reinforcement resin temperature is 240 ℃ during down with this mold injection molding, contact with the mould outermost layer from this resin, mold surface temperature (be the interface temperature of resin surface and nickel surface, or be the interface temperature of resin surface and polyimide surface) over time.Fig. 7 is that to make the polyimides layer thickness be that 0.3mm, nickel layer thickness are under the occasion of 0.02mm, the resin surface temperature over time, among the figure, solid line is the occasion of lining polyimide layer and nickel dam, dotted line is the occasion of the polyimide layer that only is covered.Under the occasion of polyimides of only being covered, the resin surface temperature reduced along with the time, and in contrast, under the occasion of lining polyimide layer and nickel dam, temperature rises after once reducing significantly once more, reduces gradually subsequently.This is that the heat of synthetic resin is absorbed by nickel dam and reduces because the thermal capacitance of the nickel on top layer is big.Therefore, the thickness of nickel dam is big more, and once the temperature amplitude of Jiang Diing is big more, and the temperature of Shang Shenging also becomes low more once more.If the temperature height of synthetic resin even then heat is absorbed by the outermost metal layer, also can fully be supplied with heat.The repeatability of the temperature appreciable impact die surface of synthetic resin.

Fig. 8 illustrates the nickel layer thickness that is covered on the polyimide layer is carried out under the occasion of various variations, and mold surface temperature is (calculated value) over time.We find, in order to make the die surface repeatability in the molding synthetic resin good, must make integrated value (Δ H) and/or (Δ h) more than certain value.Among Fig. 8, nickel layer thickness is 0.05mm, and the softening temperature of synthetic resin is that the area of representing with oblique line 2 is the integrated value shown in the present invention (Δ H) under the occasion of 105 ℃ (representing with line 1 among the figure).Locate line of picture being lower than 10 ℃ of softening temperatures (line 1), the area that this line and mold surface temperature curve surround is integrated value (Δ h).Can infer, when nickel layer thickness is 0.1mm, the temperature step-down that rises once more of the surface temperature of Jiang Diing once, the repeatability variation of die surface during injection mo(u)lding.Nickel layer thickness is under the occasion of 0.002mm, because the resin surface temperature once reduces the temperature height of rapid recovery, so the repeatability of die surface is good during injection mo(u)lding.Condition of molding necessary among the present invention is, the synthetic resin of heating is with after die surface contacts, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the integrated value (Δ H) of the value of (mold surface temperature-synthetic resin softening temperature) is more than 2 seconds ℃, and/or the integrated value (Δ h) of the value of { mold surface temperature-(synthetic resin softening temperature-10 ℃) } is more than 10 seconds ℃.

This integrated value is according to the formation of mould and difference, also according to other factors such as the kind of synthetic resin, conditions of molding and difference.When these factors when following direction develops, this integrated value increases.

The synthetic resin softening temperature reduces

The heat insulation layer thickening

The metal level attenuation

The synthetic resin temperature improves

Mold temperature improves

Moulded products thickness thickening

If develop towards these directions, then integrated value increases, and from being considered that by viewpoints such as the moulded products performance after the synthetic resin of moulding and the moulding, molding cycle times selectable scope is restricted, selects integrated value on a large scale in limited scope.

Integrated value of the present invention combines these factors, expresses the relation with the die surface repeatability.

Fig. 9～Figure 26 illustrates heat insulation layer { polyimides (representing with PI among the figure) or the epoxy resin } thickness and the lip-deep nickel layer thickness thereof that are covered on the die surface that makes steel master mould and carries out various variations, and, make moulded products thickness, the synthetic resin temperature, main mold temperature is carried out various variations and is come under the occasion of moulding, the mold surface temperature time history plot, and illustrate for various occasions, during mold surface temperature is equal to or higher than the synthetic resin softening temperature, the curve map of the relation of the integrated value Δ H of the value of synthetic resin softening temperature and (mold surface temperature-synthetic resin softening temperature) (second ℃) (calculated value).Among these figure, the integrated value of each synthetic resin softening temperature is equivalent to the integrated value described in the present invention (Δ h) for the integrated value (Δ H) described in the present invention, the integrated value of hanging down 10 ℃ temperature than softening temperature.Conclude in table 4 and the table 5 various conditions are shown, the numbering among the figure is identical with the numbering shown in table 4 and the table 5.

Table 4

NO.	The kind of resin	Moulded products thickness [mm]	PI thickness [mm]	N _iThickness [mm]	Resin temperature [℃]	Mold temperature [℃]
NO.	The kind of resin	Moulded products thickness [mm]	PI thickness [mm]	N _iThickness [mm]	Resin temperature [℃]	Mold temperature [℃]	1	HIPS	2	0.1	0.01	210	30
2	HIPS	2	0.1	0.02	210	30	1	HIPS	2	0.1	0.01	210	30
2	HIPS	2	0.1	0.02	210	30	3	HIPS	2	0.2	0.01	210	30
4	HIPS	2	0.2	0.02	210	30	3	HIPS	2	0.2	0.01	210	30
4	HIPS	2	0.2	0.02	210	30	5	HIPS	2	0.1	0.01	240	30
6	HIPS	2	0.1	0.02	240	30	5	HIPS	2	0.1	0.01	240	30
6	HIPS	2	0.1	0.02	240	30	7	HIPS	2	0.2	0.01	240	30
8	HIPS	2	0.2	0.02	240	30	7	HIPS	2	0.2	0.01	240	30
8	HIPS	2	0.2	0.02	240	30	9	HIPS	2	0.1	0.01	270	30
10	HIPS	2	0.1	0.02	270	30	9	HIPS	2	0.1	0.01	270	30
10	HIPS	2	0.1	0.02	270	30	11	HIPS	2	0.2	0.01	270	30
12	HIPS	2	0.2	0.02	270	30	11	HIPS	2	0.2	0.01	270	30
12	HIPS	2	0.2	0.02	270	30	13	HIPS	2	0.1	0.01	240	40
14	HIPS	2	0.1	0.01	240	50	13	HIPS	2	0.1	0.01	240	40
14	HIPS	2	0.1	0.01	240	50	15	HIPS	2	0.1	0.02	240	40
16	HIPS	2	0.1	0.02	240	50	15	HIPS	2	0.1	0.02	240	40
16	HIPS	2	0.1	0.02	240	50	17	HIPS	2	0.1	0.02	240	70
18	HIPS	2	0.2	0.01	240	50	17	HIPS	2	0.1	0.02	240	70
18	HIPS	2	0.2	0.01	240	50	19	HIPS	2	0.2	0.02	240	50
20	HIPS	2	0.2	0.03	240	30	19	HIPS	2	0.2	0.02	240	50
20	HIPS	2	0.2	0.03	240	30	21	HIPS	2	0.2	0.02	280	50
22	HIPS	2	0.1	0.03	240	50	21	HIPS	2	0.2	0.02	280	50
22	HIPS	2	0.1	0.03	240	50	23	HIPS	2	0.2	0.03	240	50
24	HIPS	2	0.2	0.05	240	50	23	HIPS	2	0.2	0.03	240	50
24	HIPS	2	0.2	0.05	240	50	25	HIPS	2	0.3	0.01	240	50
26	HIPS	2	0.3	0.02	240	50	25	HIPS	2	0.3	0.01	240	50
26	HIPS	2	0.3	0.02	240	50	27	HIPS	2	0.3	0.03	240	50
28	HIPS	2	0.3	0.05	240	50	27	HIPS	2	0.3	0.03	240	50
28	HIPS	2	0.3	0.05	240	50	29	HIPS	2	0.3	0.1	240	50
30	HIPS	2	0.5	0.03	240	50	29	HIPS	2	0.3	0.1	240	50

Table 5

NO.	The kind of resin	Moulded products thickness [mm]	PI thickness [mm]	N _iThickness [mm]	Resin temperature [℃]	Mold temperature [℃]
NO.	The kind of resin	Moulded products thickness [mm]	PI thickness [mm]	N _iThickness [mm]	Resin temperature [℃]	Mold temperature [℃]	31	HIPS	2	0.1	0.05	240	30
32	HIPS	2	0.1	0.05	270	30	31	HIPS	2	0.1	0.05	240	30
32	HIPS	2	0.1	0.05	270	30	33	HIPS	2	0.2	0.05	240	30
34	HIPS	2	0.2	0.05	270	30	33	HIPS	2	0.2	0.05	240	30
34	HIPS	2	0.2	0.05	270	30	35	HIPS	2	0.1	0.03	240	70
36	HIPS	2	0.2	0.02	240	70	35	HIPS	2	0.1	0.03	240	70
36	HIPS	2	0.2	0.02	240	70	37	HIPS	2	0.2	0.03	240	70
38	HIPS	3	0.2	0.02	240	50	37	HIPS	2	0.2	0.03	240	70
38	HIPS	3	0.2	0.02	240	50	39	HIPS	4	0.2	0.02	240	50
40	HIPS	5	0.2	0.02	240	50	39	HIPS	4	0.2	0.02	240	50
40	HIPS	5	0.2	0.02	240	50	41	POH	2	0.2	0.01	200	60
42	POH	2	0.2	0.02	200	60	41	POH	2	0.2	0.01	200	60
42	POH	2	0.2	0.02	200	60	43	POH	2	0.2	0.04	200	60
44	POH	2	0.3	0.02	200	60	43	POH	2	0.2	0.04	200	60
44	POH	2	0.3	0.02	200	60	45	POH	2	0.4	0.02	200	60
46	HIPS	2	0.5	0.03	240	70	45	POH	2	0.4	0.02	200	60
46	HIPS	2	0.5	0.03	240	70	47	HIPS	2	0.5	0.03	270	50
48	HIPS	3	0.5	0.03	270	70	47	HIPS	2	0.5	0.03	270	50
48	HIPS	3	0.5	0.03	270	70	49	HIPS	2	-	-	240	50
50	HIPS	2	0.1	-	240	50	49	HIPS	2	-	-	240	50
50	HIPS	2	0.1	-	240	50	51	HIPS	2	0.2	-	210	30
52	HIPS	2	0.2	-	210	50	51	HIPS	2	0.2	-	210	30
52	HIPS	2	0.2	-	210	50	53	HIPS	2	0.2	-	240	30
54	HIPS	2	0.2	-	240	50	53	HIPS	2	0.2	-	240	30
54	HIPS	2	0.2	-	240	50	55	HIPS	2	0.2	-	270	30
56	HIPS	2	0.2	-	270	50	55	HIPS	2	0.2	-	270	30
56	HIPS	2	0.2	-	270	50	57	HIPS	2	0.3	-	240	50
58	HIPS	2	1.0	-	240	50	57	HIPS	2	0.3	-	240	50
58	HIPS	2	1.0	-	240	50	59	HIPS	2	0.3	0.002	240	50
60	HIPS	2	0.3	0.005	240	50	59	HIPS	2	0.3	0.002	240	50
60	HIPS	2	0.3	0.005	240	50	61	HIPS	3	0.2	0.02	240	30
62	HIPS	4	0.2	0.02	240	30	61	HIPS	3	0.2	0.02	240	30
62	HIPS	4	0.2	0.02	240	30	63	HIPS	2	0.5	-	240	50
64	HIPS	2	Pottery 0.3	-	240	50	63	HIPS	2	0.5	-	240	50
64	HIPS	2	Pottery 0.3	-	240	50	65	HIPS	2	Pottery 0.3	-	240	35
66	HIPS	3	Epoxy resin 0.3	0.03	200	40	65	HIPS	2	Pottery 0.3	-	240	35

Fig. 9～Figure 22 is for being that PI, synthetic resin are the calculated value of polystyrene rubber reinforcement (HIPS) for heat insulation layer, Figure 23～Figure 24 is for being that PI, synthetic resin are the calculated value of polyformaldehyde (POM) with crystallization latent heat for heat insulation layer, and Figure 25 is ceramic (ZrO for heat-insulating material ₂/ Y ₂O ₃), synthetic resin is the calculated value of HIPS, Figure 26 is for being that epoxy resin, synthetic resin are the calculated value of HIPS for heat insulation layer.

From these figure, can clearly find out the integrated value when under the mould that various layers constitute, various condition of molding, carrying out moulding.That is, the calculating of the integrated value shown in the present invention must can easily be read the big probable value of this integrated value with calculating computer from the various data shown in Fig. 4～Figure 26.

Use polyimides and epoxy resin as heat insulation layer shown in the figure, use nickel dam as metal level, use other heat resistant polymers as heat-insulating material, use as metal under the occasion of nickel other metals such as chromium in addition, also can from Fig. 4～data shown in Figure 26, infer.

When the temperature of synthetic resin shown in Figure 18～Figure 21 changes, the variation of mold surface temperature and the variation of integrated value.The synthetic resin temperature improves, and then integrated value enlarges markedly.That is, heat insulation layer and metal level are synthesized resin supply heat and heat up, and the temperature and time of this rising increases integrated value, and the die surface repeatability of moulded products is good.This common metal mould with the heat insulation layer that is not covered is significantly different.That is, the common metal mould as shown in Figure 1, when synthetic resin contacted with the die surface that is cooled, surface layer of synthetic resin was cooled to identical with mold temperature immediately.Even rising synthetic resin temperature is too, the effect that the synthetic resin temperature is improved.With common die and during moulding in rising synthetic resin temperature, the effect that viscosity reduces, injection pressure is conducted to the moulded products end with synthetic resin, the die surface repeatability of moulded products has some improvement, but the sort of effect that does not have the present invention to obtain, promptly, mold surface temperature is risen within a certain period of time, integrated value Δ H, integrated value Δ h are increased, significantly improve the repeatability of die surface thus.Among the present invention, improve the synthetic resin temperature and carry out moulding, have the effect that integrated value enlarges markedly, this point is different fully with the occasion of using common die.

Among the present invention,, must specify synthetic resin temperature and main mold temperature at least along with different these effects of condition of molding are significantly different.Especially, the effect of resin temperature is remarkable, introduces integrated value Δ H, the Δ h as parameter that comprises this factor in the present invention, makes the present invention and known document that evident difference be arranged.

Figure 25 illustrates as heat-insulating material and uses the occasion of pottery and the occasion of use epoxy resin.Introduction is as the pottery of heat-insulating material, but the thermal conductivity ratio heat resistant polymer of pottery is much bigger, uses as heat-insulating material under the occasion of pottery, and as shown in figure 25, mold surface temperature reduces rapidly, and integrated value is minimum, can not use pottery among the present invention.

It is 0.5mm when above that Figure 26 illustrates heat insulation layer thickness, is difficult to satisfy condition of the present invention, that is, contact with die surface within 5 seconds at synthetic resin, and mold surface temperature is reduced to below the synthetic resin softening temperature.

The contrast that mold surface temperature shown in Fig. 6 of the variation that Figure 27 illustrates mold surface temperature in the forming method of the present invention and the known document US P 5,388,803 that quotes changes.In the citing document, synthetic resin contacts the back in the time of about 20 seconds with die surface, and mold surface temperature is reduced to below the glass transition temperature of synthetic resin, and among the present invention, is reduced to below the glass transition temperature in 5 seconds.The invention provides a kind of forming method, wherein, mold surface temperature shortens the molding cycle time, economical thus being reduced to after 5 seconds below the glass transition temperature of synthetic resin.

Figure 31 illustrates and changes resin temperature carries out the occasion compacted under goods of injection mo(u)lding with polystyrene rubber reinforcement (STYRON 495 Asahi Chemical Industries industry (strain) system trade name) glossiness.The glossiness of using among the present invention is measured under reflection angle 60 degree according to JIS K7105.As 100%, so the glossiness of molding synthetic resin goods also can surpass 100% to this glossiness with the mirror surface luster of the glass surface of refractive index 1.567.Glossiness hereinafter adopts this assay method to measure.Compare with the occasion with the common die moulding of no heat insulation layer, be covered under the formed in mould occasion with heat insulation layer, along with the resin temperature difference, the glossiness of moulded products alters a great deal.

Figure 32 illustrates under the occasion of using polystyrene rubber reinforcement (STYRON 495 Asahi Chemical Industries industry (strain) system trade name), the relation of integrated value (Δ H) and moulded products glossiness.The glossiness of injection-molded item is according to injection mo(u)lding speed and difference, and injection speed is more little, and glossiness is low more.Injection speed is low more, and effect of the present invention is remarkable more, can advantageously use.Among the present invention, be 20～300mm/ second, carry out moulding under the condition of preferred 30～200mm/ second in the average flow velocity of synthetic resin in die cavity.The value of the glossiness of Figure 32 under the 50mm/ condition of second, carrying out injection mo(u)lding.Shown in the example of injection-molded item among Figure 32, among the present invention, if integrated value (Δ H) is more than 2 seconds ℃, then the die surface repeatability is good, the moulded products glossiness is good, if integrated value (Δ H) is that then glossiness is better more than 5 seconds ℃, if integrated value (Δ H) is more than 7 seconds ℃, then glossiness is almost near 100%.

Figure 33 illustrates and uses same polystyrene rubber reinforcement (STYRON 495 Asahi Chemical Industries industry (strain) system trade name) the occasion lower integral value (Δ h) of injection mo(u)lding and the relation of injection-molded item glossiness.If integrated value (Δ h) is more than 10 seconds ℃, then the die surface repeatability is good, and the moulded products glossiness is good, if integrated value (Δ h) is that then glossiness is better more than 12 seconds ℃, if integrated value (Δ h) is more than 15 seconds ℃, then glossiness is almost near 100%.

The glossiness that the objective of the invention is to obtain polystyrene rubber reinforcement as shown in the figure is more than 80%, and is preferred 90%, more preferably the high gloss moulded products more than 95%.In order to be used for not applying on the moulded products, requiring the purposes of outward appearance, just require the outward appearance of this degree.Self-evident, even 2 seconds ℃ of integrated value (Δ H) less thaies, perhaps integrated value (Δ h) less than is 10 seconds ℃, its glossiness also obtains corresponding improvement, but in order to obtain high glaze moulded products and the significant minimum moulded products of weld bond, must make integrated value (Δ H) is more than 2 seconds ℃, and/or integrated value (Δ h) is more than 10 seconds ℃.We find can stipulate with integrated value shown in the present invention (Δ H) and/or integrated value (Δ h) glossiness of moulded products, so far finish the present invention.If heat insulation layer thickness is increased, can obtain the moulded products of good appearance, still, the increase of heat insulation layer thickness makes the molding cycle time elongated, considers it is inappropriate from the shaping efficiency aspect.The present invention is a kind of method that makes outward appearance improvement and molding cycle time compatibility.

Figure 34 illustrates the be not covered common metal mould of heat insulation layer of use, making the die surface that constitutes die cavity is mirror-like, under the occasion with polystyrene rubber reinforcement (105 ℃ of STYRON 495 vicat softening temperatures) injection mo(u)lding, the relation of mold temperature and moulded products glossiness.Die surface repeatability during moulding is estimated with the glossiness of moulded products.The repeatability of die surface, promptly the glossiness of moulding goods is different along with the injection speed (flowing velocity of synthetic resin in mould) of synthetic resin, when mold temperature be (a synthetic resin softening temperature-10 ℃), has nothing to do with injection speed and almost constant.If mold temperature improves, the glossiness of its corresponding moulded products improves, and in order to make glossiness near 100%, must make mold temperature be increased to softening temperature near the synthetic resin of moulding.But as shown in figure 34, if mold temperature is increased to 95 ℃ of the temperature of (105 ℃-10 ℃ of synthetic resin softening temperatures), the moulded products glossiness becomes fairly good, near the glossiness 95% that is called the category-A surface.Even (Δ H) is little for integrated value, if integrated value (Δ h) enlarges markedly, then the die surface repeatability is good equally.During the heat insulation layer thickening, the ratio of { integrated value (Δ h)/integrated value (Δ H) } increases.Therefore find, stipulate the repeatability of die surface both ways, can stipulate actual result well in integrated value (Δ H) and integrated value (Δ h).We just are this with the reason that these two kinds of integrated values are decided to be parameter.The numerical value of glossiness described herein is relative all the time, synthetic resin to original outward appearance extreme difference, perhaps to the synthetic resin of original bad order, high gloss numerical value is low relatively, compare with the moulded products that uses the past common die, if significantly improved outward appearance, then as the high gloss moulded products described in the present invention.

Figure 35 illustrates the heat insulation layer of the mould described in the present invention and the interface of metal level is the state of micro concavo-convex shape ground driving fit.The closing force of preferred heat insulation layer and metal level is big, preferably fills up generation anchor effect mutually by heat insulation layer and metal level on its interface closing force is increased.Preferred micro concavo-convex degree is in datum length is 80 μ m, the interface of metal level and heat insulation layer concavo-convex is 0.5～10 μ m from the difference of the mean value of the summit absolute altitude of 5 projectioies of a projection to the and the mean value of the lowest point absolute altitude that is recessed into the 5th depression from.Because concavo-convex intricately described herein is filled up the shape that produces the anchor effect mutually, rather than simple concavo-convex, so absolute altitude is selected each the darkest concavo-convex position.

Figure 36 and Figure 37 illustrate the inventive method are used for moulding biconvex lens and Fresnel lens etc.Figure 36 illustrates with Fresnel lens in the past, the state of injection mo(u)lding under common condition of molding.Among Figure 36, have on the die surface of metal die 3 and protrude angle 5 and depression angle 6, generally speaking, injected synthetic resin 4 can not enter into the depths 7 at depression angle 6 fully, can not get fully reproducing the lens in bight.

Figure 37 illustrates the Fresnel lens die with the inventive method moulding.Among Figure 37, heat insulation layer 9 is arranged on the surface of main mould 8, and the metal level 10 that also has the Fresnel lens shape is gone up on its surface.The die surface repeatability of common Fresnel lens die is poor especially, is depression angle 6 as shown in the figure, and the effect of heat insulation layer 9 is good in the die surface repeatability at depression 6 places, angle.Therefore, among the present invention, use the mould of Fresnel lens and biconvex lens, metal layer thickness adopts the thickness 12 at thin-walled position.This metal layer thickness 12 is below 1/3 of heat insulation layer thickness 11, and is preferred below 1/5, is 0.001～0.1mm, and this metal level must with the heat insulation layer driving fit.

Forming method of the present invention is, use layer on surface of metal or part metals laminar surface for the mould on the delustring shape surface of multistage blasting treatment of process and/or the formation of multistage etch processes carries out moulding, obtain the good moulded products of marresistance with micro concavo-convex shape delustring shape surface.

Figure 38 illustrates the good delustring shape moulded products (38-1) of the marresistance of making of forming method of the present invention and with the cross section of the delustring shape moulded products (38-2) that easily is scratched of the method moulding of passing by.The moulded products of the usefulness the inventive method moulding (38-1), the recess top 15 on the micro concavo-convex surface of molding synthetic resin goods 13 is an acute angle, protuberance top 14 is circular, is difficult to be scratched.In contrast, (38-2) moulded products in the past shown in, on the protuberance top 16 with recess top 15 be all acute angle, nail is under the occasion that rubs on the moulded products surface, protuberance top 16 is subject to grinding and scratches.The plastic moulded products that goes out shown in figure (38-1) of forming method of the present invention because the ratio that this product surface protuberance top is an acute angle is few, therefore is difficult to by scratches such as nails.

Example with the injection-molded item shown in Figure 39 describes in more detail.Among Figure 39, walk around hole 18 by the synthetic resin of cast gate 17 injections and flow, be integrated, form weld bond 19 at weld.Among Figure 39, when using the mold injection molding of the metal level that has the micro concavo-convex surface on be covered on the die surface heat insulation layer and its surface, the micro concavo-convex surface of metal level is copied on the moulded products surface.But, if use when the used sand-blast of general delustring processing carries out the heat insulation layer lining mold injection molding of micro concavo-convexization, then the weld of moulded products 20 to the micro concavo-convex degree in the zone (the following weld 21 that abbreviates as in description of drawings) of the resin flows end becomes big, during with the resin forming of black, weld 21 blackouts, general part 22 is turned white, and is difficult to obtain the moulded products of the even glossiness described in the present invention.Its reason is presumed as follows.With Figure 40 and Figure 41 its reason is described.

In the injection mo(u)lding of the moulded products shown in Figure 39, the pressure that weld 21 and general part 22 are subjected to the die cavity wall typically is shown among Figure 40.Among Figure 40, the general part 22 suffered pressure of moulded products are curve 23, and weld 21 suffered pressure are curve 24.Curve 25 is the suffered pressure in cast gate position.That is, general part 22 suffered pressure slowly rose along with inject time, and the suffered pressure of weld 21 synthetic resin be subject to a high pressure when the die cavity wall contacts.As shown in Figure 8, heated synthetic resin contacts with the die cavity wall of heat insulation layer, has heated heat insulation layer lining surface, begins to cool down immediately.In the mould of the lining 0.05mm nickel dam of Fig. 8, after 1.5 seconds, mold surface temperature is reduced to below 105 ℃.In order to reproduce die surface better, heated synthetic resin is with when the die cavity wall contacts, and resin is subject to a high pressure, that is, when the skin section branch of die cavity wall and synthetic resin is in high temperature, preferably make resin be subjected to high pressure.As shown in figure 40, be subjected to high pressure at synthetic resin with resin when the die cavity wall contacts, weld can more correctly reproduce the micro concavo-convex of die cavity wall.

With Figure 41 this process is described typically.Among the 41-1, die surface is made of the metal level 27 of heat insulation layer 26 and its lip-deep micro concavo-convex shape.There is acute angle recess 28 at the micro concavo-convex place on surface.When carrying out injection mo(u)lding with this mould, the general part of moulded products contacts with the die cavity wall from synthetic resin 29, resin pressure slowly rises, therefore, in the pressure uphill process, die cavity wall and resin surface layer cooling, synthetic resin can not enter into the depths of the micro concavo-convex of die cavity wall, the position 30 (41-2) that appearance can not be filled.In contrast, at the moulded products weld, rise with resin pressure when the die cavity wall contacts at synthetic resin 29, therefore, synthetic resin can enter into the depths (41-3) of the micro concavo-convex of mould.Its result, weld 21 is compared with general part 22, and it is big that the concave-convex surface degree of moulded products becomes, and the synthetic resin of black turns black at weld, can not form uniform delustring state.

This phenomenon appears under the occasion with heat insulation layer lining mold injection shaping delustring shape moulded products significantly.The invention provides a kind of product molding method that improves this bad phenomenon.Even for the weld that makes moulded products with the concave-convex surface of general part, must make the micro concavo-convex on heat insulation layer surface form appropriate concaveconvex shape.Moulded products with simple shape shown in Figure 39 illustrates the present invention, the shell of light current machine etc. has the complicated shape with the moulding of many cast gates, in the goods of this complicated shape, general part difference occurs with the dullness of weld, in addition, under a lot of occasions, difference appears in the dullness of the weld bond left and right sides.This occasion that difference appears in the weld bond left and right sides is that left and right sides resin flow speed difference causes.The side that flowing velocity is fast, resin are subjected to resin pressure early with after the die cavity wall contacts, the side that flowing velocity is slow, and resin is with after the die cavity wall contacts, and it is later to be subjected to resin pressure, and like this, the left and right sides easily produces the difference of die surface repeatability.The present invention is effective especially under this occasion.

Shown in Figure 42, Figure 43, Figure 44 and Figure 45 with the preferred embodiment of method mfg. moulding die of the present invention.Among Figure 42, exist the thick heat insulation layer of 0.05～2.0mm 26 on the surface of metal system master mould 32, attaching the very strong coating metal layer of closing force on it, again 2 layers of metal level 33,34 of lining on this surface.Because the closing force of this heat insulation layer and metal level is very strong, therefore to compare with metal level 33,34, coating metal layer can be quite thin, has been omitted in Figure 42～Figure 45.The whole metal layer thickness that comprises metal level 33,34 adds up to below 1/3 of heat insulation layer 26 thickness, and is 0.01～0.5mm.The closing force of heat insulation layer and metal level is strong, and the metal level that attaches on the coating metal layer constitutes by 2 layers, and the thickness of surface metal-layer 34 is preferably more than 1/2 of metal level gross thickness, more preferably more than 2/3.The thickness of inboard metal level 33 is preferably 0.002～0.1mm, more preferably 0.003～0.05mm.The etching speed of surface metal-layer 22 is more than 2 times of its inboard metal level 33, is preferably more than 3 times, more preferably more than 5 times.This mould is carried out etch processes,, obtain the mould that the present invention shown in (42-2) requires by the main surface metal-layer 2 of etch processes optionally.

Illustrate in greater detail the employing etch processes among Figure 43 and Figure 44, make the die surface metal level become the method for the delustring shape of requirement of the present invention.Among Figure 43, lining heat insulation layer 26 (43-1) on the die cavity wall that constitutes metal system master mould 32 die cavities.Then, on the surface of this heat insulation layer 26, be covered coating metal layer (omitting among the figure) and 2 layers of metal level 35,36 (43-2).The etching speed of the surface metal-layer 36 of metal level is preferably more than 2 times of inboard metal level 35 etching speeds, more preferably more than 3 times, most preferably is more than 5 times.Lining photoresist 37 (43-3) on the surface of this metal level 36.Then, cover with shielding film 38.Shine with ultraviolet ray, make the photoresist at illuminated position solidify (43-4).Then, the photoresist of uncured portion cleaned remove, stay the cured resin 39 (43-5) of pattern-like.Then, adopt will the not be covered metal level of part of cured resin 39 of etch processes to dissolve, form the die surface (43-6) of metal level 36 with concavo-convex surface.The operation of photoresist (43-3) to etching (43-6) repeats to be covered.

The multistage etching work procedure that is etched to below 2 grades shown in Figure 44.Among Figure 44, first order etching is to form upward lining photoresist 37 (44-2) of concavo-convex surface metal-layer 26 (44-1), carrying out pattern in its surface covers, exposure, development, clean back (44-3), be etched into concavo-convex (44-4) again, repeat (44-2) operation, obtain the mould (44-5) that the present invention requires to (44-4) operation.Be etched to the good inboard metal level 35 of elching resistant, so etching speed slows down, the bottom that makes the metal level recess can not form the acute angle recess for circular.With the mold injection molding shown in (44-5), can obtain the good moulded products of marresistance that the present invention that figure (38-1) illustrates requires.

Shown in Figure 43 and Figure 44 on the whole surface of mould photosensitive resin coating, cover the method for exposing with shielding film, Figure 45 illustrates preferred method.Among Figure 45, photoresist resembled reserve the compartment of terrain being sprinkling upon on the layer on surface of metal and sporadicly be coated with, make its curing (45-1), then adopt etch processes to make surface metal-layer 36 form concavo-convex (45-2) with the ultraviolet ray irradiation.Repeat fragmentary coating, ultraviolet ray irradiation (45-3) and the etch processes (45-4) of this photoresist, this operation is repeated to obtain the delustring shape surface mold (45-5) that the present invention requires for several times again.Among the present invention, photoresist painting process to etching work procedure preferably repeats 3～10 times, and more preferably 4～8 times, the micro concavo-convex surface of formation preferable shape.Also comprise among the present invention, on the die surface that adopts multistage etch processes of the present invention to obtain with micro concavo-convex shape frosting, attach the thin layer corrosion resistant metal layer that this micro concavo-convex shape is significantly changed, can improve the durability in the injection mo(u)lding so effectively.

Below further specify the present invention with embodiment and comparative example.

In embodiment and the comparative example, use following main mould, heat insulation layer, metal level and synthetic resin.

Main mould: be the die injection moulding of steel (S55C) system.The thermal coefficient of expansion of this mould is 1.1 * 10 ^-5/ ℃.Die cavity with moulded products shown in Figure 39 20.Product size is 100mm * 100mm, thick 2mm, and central authorities have the hole 4 of 30mm * 30mm.Cast gate 17 is a side gate shown in Figure 39, produces weld bond 19 on the moulded products 20.Die surface is a mirror-like.Prepare 19 and form the nested of this main mold cavity, on the surface that respectively is nested to form die cavity, carry out hard chromium plating.

Heat insulation layer A: primary coat is carried out on the nested surface of main mould handled.Be coated with the polyimides precursor solution of one deck as containing of silane coupling agent of a large amount of CO groups thinly, heating makes it form polyimide coating as priming coat.Be coated with one deck polyimide varnish (Torayneece#3000Toray Industries thereon, Inc. (strain) system trade name), 160 ℃ of heating down, repeat this coating and heating operation then, form the thickness of regulation, then 290 ℃ down heating make it 100% be converted into acid imide, form the polyimide layer of specific thickness.The closing force of polyimide layer and main mould is 1kg/10mm.

Heat insulation layer B: primary coat is carried out on the nested surface of main mould handled.Be coated with the polyimides precursor solution of one deck as containing of silane coupling agent of a large amount of CO groups thinly, heating makes it form polyimide coating as priming coat.Be coated with one deck polyimide varnish (Torayneece#3000Toray Industries thereon, Inc. (strain) system trade name), 160 ℃ of heating down, repeat this coating and heating operation then, form the thickness of regulation, at last, coating one deck is added into the last also thin layer of the compound polyimide varnish of abundant mixing formation of titanium oxide fine powder that average grain diameter is 0.1 μ m in the ratio of solid component content 20 weight % on the outermost surface of heat insulation layer, then 290 ℃ down heating make it 100% be converted into acid imide, forming outermost layer is the polyimide layer of the specific thickness of the thick compound polyimide layer of 10 μ m.The closing force of polyimide layer and main mould is 1kg/10mm.

Metal layer A: etch processes is carried out on the heat insulation layer surface with the strong acid solution that contains chromic acid, then, handle by the order that neutralization → sensitiveness processing → activity is handled, use sodium hypophosphite as reducing agent then, under 35 ℃ of low temperature and weak base state, low speed ground carries out chemical nickel plating, and forming phosphorus content is the chemical nickel coating of 3～4 weight %.

Metal level B: as reducing agent, carry out chemical nickel plating with sodium hypophosphite under 60 ℃ and acid state, forming phosphorus content is the chemical Ni-plating layer of 6～7 weight %.

Metal level C: sulfur content is the electrolytic nickel coating of 0.005 weight %.

The thermal coefficient of expansion of above-mentioned various nickel coatings is all about 1.3 * 10 ^-5/ ℃.

Metal level D: hard chrome plating.The case hardness of this coating is HV1000.

The synthetic resin of injection mo(u)lding:

(a): polystyrene rubber reinforcement (STYRON 495 Asahi Chemical Industries industry (strain) system trade name), 105 ℃ of glass transition temperatures.

(b): the SAN resin (STYRAC-A SGF R160T, Asahi Chemical Industry's industry (strain) system, trade name) that adds 30 weight % glass fibres.The vicat softening temperature of base resin is 110 ℃.Glass fibre in the synthetic resin is an E-glass, and its hardness is HV640.

(c): SAN resin (STYRAC-AS767, Asahi Chemical Industry's industry (strain) system, trade name).110 ℃ of vicat softening temperatures.

Injection mo(u)lding condition: be shown in table 6.Resin flows speed in the mould is 50mm/ second when not indicating.

The assay method of glossiness: JIS K7105,60 ° of angles of reflection. Embodiment 1～7 and comparative example 1～7

On the heat insulation layer surface of the main mould of lining heat insulation layer B, the thick metal layer A of lining 0.0005mm, coated metal layer C becomes mirror-like with this surface grinding in its surface, the heat insulation layer of making polyimides (PI) layer with all thickness shown in the table 6 and nickel (Ni) the layer mould that is covered.The closing force of the closing force of metal level and heat insulation layer and heat insulation layer and main mould all is equal to or higher than 0.5kg/10mm.Use this mould under each condition of molding shown in the table 6, to carry out the injection mo(u)lding of synthetic resin (a).The integrated value of each condition of molding and the glossiness of moulded products are shown in Table 6.

Table 6

	Mould		Condition of molding		Integrated value			Moulded products glossiness %
	Mould		Condition of molding		Integrated value				PI mm	Ni mm	Resin temperature ℃	Mold temperature ℃	Condition table No.	ΔH ℃·sec.	Δh ℃·sec.
	Embodiment 1	0.2	0.01	240	30	7	4		PI mm	Ni mm	Resin temperature ℃	Mold temperature ℃	Condition table No.	ΔH ℃·sec.	Δh ℃·sec.	9.1	98
Embodiment 2	Embodiment 1	0.2	0.01	240	30	7	4	0.2	0.02	240	30	8	2.8	7.7	96	9.1	98
Embodiment 2	Embodiment 3	0.1	0.01	270	30	9	2.3	0.2	0.02	240	30	8	2.8	7.7	96	4	85
Embodiment 4	Embodiment 3	0.1	0.01	270	30	9	2.3	0.2	0.01	270	30	11	10.6	17.3	103	4	85
Embodiment 4	Embodiment 5	0.2	0.02	270	30	12	8.3	0.2	0.01	270	30	11	10.6	17.3	103	16	101
Embodiment 6	Embodiment 5	0.2	0.02	270	30	12	8.3	0.1	0.01	240	50	14	2.3	4.6	95	16	101
Embodiment 6	Embodiment 7	0.2	0.03	240	50	23	7.2	0.1	0.01	240	50	14	2.3	4.6	95	17	103
Comparative example 1	Embodiment 7	0.2	0.03	240	50	23	7.2	0.1	0.01	210	30	1	-	0.5	25	17	103
Comparative example 1	Comparative example 2	0.1	0.02	210	30	2	-	0.1	0.01	210	30	1	-	0.5	25	0.2	23
Comparative example 3	Comparative example 2	0.1	0.02	210	30	2	-	0.2	0.01	210	30	3	0.6	3.4	46	0.2	23
Comparative example 3	Comparative example 4	0.2	0.02	210	30	4	-	0.2	0.01	210	30	3	0.6	3.4	46	2	43
Comparative example 5	Comparative example 4	0.2	0.02	210	30	4	-	0.1	0.01	240	30	5	0.9	2	65	2	43
Comparative example 5	Comparative example 6	0.1	0.02	240	30	6	0.3	0.1	0.01	240	30	5	0.9	2	65	1.3	48
Comparative example 7	Comparative example 6	0.1	0.02	240	30	6	0.3	0.1	0.02	270	30	10	1.4	3.4	68	1.3	48

The integrated value of embodiment 1～7 (Δ H) is more than 2 seconds ℃, and/or integrated value (Δ h) is more than 10 seconds ℃.After contacting 5 seconds with die surface, mold surface temperature all is reduced in arbitrary embodiment below (synthetic resin softening temperature-20 ℃).The glossiness height of each moulded products of embodiment, weld bond are unshowy yet, and good appearance is known as the category-A surface.Heat insulation layer can not take place in 10,000 injection mo(u)ldings yet or metal level is peeled off even carry out with the mould of embodiment 3.The heat insulation layer of embodiment shown in Figure 35 3 and metal level are at the sectional view of joint interface.Metal level and heat insulation layer have the effect of anchor with the driving fit mutually of micro concavo-convex interface. Embodiment 8

Outermost metal layer C to mould shown in the embodiment 7 carries out etching and processing, and forming recess depths is the pattern of the leather patterns shape of 0.02mm.The protuberance of this layer on surface of metal pattern is a minute surface, and recess is delustring shape surface.Carry out the injection mo(u)lding identical with this mould, can obtain that tangible weld bond is few, good appearance, have the moulded products on pattern shape surface with embodiment 7.The layer on surface of metal of this leather patterns shape, (Δ H) is identical with embodiment 7 for the integrated value of its protuberance, is 7.2 seconds ℃, and integrated value (Δ h) is 17 seconds ℃.After synthetic resin contacted 5 seconds with die surface, mold surface temperature was reduced to below (synthetic resin softening temperature-20 ℃). Embodiment 9

Use a kind of like this heat insulation layer lining mould, on the heat insulation layer surface of the main mould of lining 0.3mm heat insulation layer B, the thick metal layer A of 0.5 μ m that is covered, the metal level B of the 10 μ m that are covered in its surface, surface grinding is become mirror-like, and then the metal level D of the 10 μ m that are covered.The closing force of the closing force of metal level and heat insulation layer and heat insulation layer and main mould all is equal to or higher than 0.5kg/10mm.Under the condition of 240 ℃ of resin temperatures, 50 ℃ of main mold temperatures, with synthetic resin (b) injection mo(u)lding.The synthetic resin of heating is with after die surface contacts, and during mold surface temperature was equal to or higher than the synthetic resin softening temperature, the integrated value (Δ H) of the value of (surface temperature-synthetic resin softening temperature) was more than 5 seconds ℃.In 1000 injection mo(u)ldings of synthetic resin, die surface is not scratched, and the die surface repeatability of moulded products is also fine, and the glossiness height of the moulded products of acquisition, showy weld bond are few.After synthetic resin contacted 5 seconds with die surface, mold surface temperature was reduced to below (synthetic resin softening temperature-20 ℃). Comparative example 8

Use on main mould, be covered the heat insulation layer A of 0.3mm, surface grinding become the heat insulation layer lining mould of mirror-like.Order by synthetic resin (c), (b) is carried out injection mo(u)lding.Condition of molding is 240 ℃ of resin temperatures, 50 ℃ of main mold temperatures.In 1000 injection mo(u)ldings of synthetic resin (c), the heat insulation layer surface is not scratched, but in the injection mo(u)lding of synthetic resin (b), the heat insulation layer surface is scratched in 100 moulding, and glossiness is lower than 20%. Embodiment 10

On the heat insulation layer surface of the main mould of lining 0.2mm heat insulation layer B, the thick metal layer A of lining 0.0005mm, the metal level B of the 0.01mm that is covered in its surface, the thick metal level C of lining 0.03mm on this surface again.This mould is adopted 6 grades of etch processes shown in Figure 45, obtain delustring shape surface mold of the present invention.Carry out the injection mo(u)lding of synthetic resin (a) with the mould of the present invention that obtains.The injection mo(u)lding condition is 240 ℃ of resin temperatures, 40 ℃ of mold temperatures.Injection-molded item does not have showy weld bond, and general part is uniform delustring face with weld, and its glossiness is below 20%, carries out pencil test with the pencil of 2B hardness, does not have showy cut.The concaveconvex shape on the surface of injection-molded item shown in Figure 46.Concaveconvex shape is measured with the accurate rough surface shapometer of producing " Surfcomb 570A " in (strain) Tokyo.In the concaveconvex shape on injection-molded item surface, the acute angle protuberance that protrudes on the surface is few, and this surface configuration is difficult to be scratched.

The polyimides that is covered on the main mould of lining 0.2mm heat insulation layer A in contrast to this below is shown, 1 grade of blasting treatment is carried out on the surface of this lining mould, form the occasion on delustring shape surface.

Use the polyimides lining mould of this surface, carry out the injection mo(u)lding of same synthetic resin as the micro concavo-convex shape.The weld bond depression of moulded products does not have showy weld bond less than 1 μ m, but on the dullness of general part 22 and weld 21 difference is arranged, and is difficult to become the moulded products of even delustring shape.The pattern of concave-convex surface shown in Figure 47.The concave-convex surface pattern of the lining of polyimides shown in Figure 47-1 mould, the concave-convex surface pattern of the general part of moulded products shown in Figure 47-2, the concave-convex surface pattern of moulded products weld 5 shown in Figure 47-3.The general part 22 of moulded products is obviously different with the concave-convex surface pattern of weld 21.The frosting of weld 21 carries out pencil test with the pencil of 2B hardness and easily is scratched.

Utilize possibility on the industry

Carry out injection mo(u)lding or the blow molding of synthetic resin with heat insulation layer coating mould of the present invention, can obtain the good moulded products of outward appearance. Produced a large amount of weld bonds, the light current machine of rear processing or the various injection-molded items such as shell of office equipment such as must apply for the past, adopt forming method of the present invention to carry out moulding, make the repeatability of die surface good, obvious weld bond is few, can save the rear processing such as coating, be very cost-effective. Owing to saved coating, make the recovery of synthetic resin easier, the organic solvent that disperses during coating in atmosphere reduces, and is very favourable to environmental protection.

And, when making the crystallinity molding synthetic resin with method of the present invention, can obtain economically until form the moulded products of crystallization near the moulded products near surface. Until close moulded products near surface forms the moulded products of crystallization, good at aspects such as case hardness, abrasion performance and platings.

Claims

1. the forming method of a synthetic resin comprises

And the following condition of molding moulding of employing:

2. the injection molding forming method of a synthetic resin comprises

And the following condition of molding moulding of employing:

3. the injection molding forming method of a synthetic resin comprises

And the following condition of molding moulding of employing:

4. the injection molding forming method of synthetic resin of record in the claim 2, wherein, heat insulation layer thickness is 0.1mm～0.4mm, metal layer thickness be lower than heat insulation layer thickness 1/3 and be 0.001～0.07mm, and adopt a kind of like this condition of molding injection mo(u)lding, promptly, integrated value (Δ H) is 2 seconds ℃～50 seconds ℃, and/or integrated value (Δ h) is 10 seconds ℃～100 seconds ℃, and after synthetic resin contacted 5 seconds with die surface, and mold surface temperature is reduced to below (synthetic resin softening temperature-10 ℃).

5. the injection molding forming method of synthetic resin of record in the claim 2, wherein, heat insulation layer thickness is 0.12mm～0.3mm, metal layer thickness is 1/100～1/5 of a heat insulation layer thickness, and be 0.002～0.06mm, and a kind of like this condition of molding injection mo(u)lding of employing, promptly, integrated value (Δ H) is 5 seconds ℃～40 seconds ℃, and/or integrated value (Δ h) is 12 seconds ℃～70 seconds ℃, and after synthetic resin contacted 5 seconds with die surface, mold surface temperature was reduced to below (synthetic resin softening temperature-10 ℃).

6. the injection molding forming method of synthetic resin of record in the claim 3, wherein, heat insulation layer thickness is 0.1mm～0.4mm, the protuberance metal layer thickness is lower than 1/3 of heat insulation layer thickness, and be 0.01～0.07mm, the recess depths of decorative pattern shape is 0.005～0.06mm, and a kind of like this condition of molding injection mo(u)lding of employing, promptly, integrated value (Δ H) is 2 seconds ℃～50 seconds ℃, and/or integrated value (Δ h) is 10 seconds ℃～100 seconds ℃, and after synthetic resin contacted 5 seconds with die surface, and mold surface temperature is reduced to below (synthetic resin softening temperature-10 ℃).

7. the injection molding forming method of synthetic resin of record in the claim 3, wherein, heat insulation layer thickness is 0.12mm～0.3mm, the protuberance metal layer thickness is lower than 1/5 of heat insulation layer thickness, and be 0.01～0.06mm, the recess depths of decorative pattern shape is 0.005～0.04mm, and a kind of like this condition of molding injection mo(u)lding of employing, promptly, integrated value (Δ H) is 5 seconds ℃～40 seconds ℃, and/or integrated value (Δ h) is 12 seconds ℃～70 seconds ℃, and after synthetic resin contacted 5 seconds with die surface, and mold surface temperature is reduced to below (synthetic resin softening temperature-10 ℃).

8. the injection molding forming method of synthetic resin of record in the claim 2 or 3, adopting synthetic resin average flow velocity in mould is 20～300mm/ condition injection mo(u)lding of second.

9. the blow molding method of a synthetic resin comprises

And the following condition of molding moulding of employing:

10. the blow molding method of synthetic resin of record in the claim 9, wherein, heat insulation layer thickness is 0.2mm～0.5mm, metal layer thickness is 1/100～1/5 of a heat insulation layer thickness, and be 0.004～0.06mm, and adopt a kind of like this condition of molding blow molding, promptly, integrated value (Δ H) is 20 seconds ℃～100 seconds ℃, and/or integrated value (Δ h) is 30 seconds ℃～300 seconds ℃.

11. the blow molding method of a synthetic resin comprises

And the following condition of molding moulding of employing:

12. the forming method of the synthetic resin of record in the claim 11, wherein, heat insulation layer thickness is 0.2mm～0.5mm, the protuberance metal layer thickness is 1/100～1/5 of a heat insulation layer thickness, and is 0.01～0.08mm, and the recess depths of decorative pattern shape is 0.005～0.07mm, and a kind of like this condition of molding blow molding of employing, that is, integrated value (Δ H) is 20 seconds ℃～100 seconds ℃, and/or integrated value (Δ h) is 30 seconds ℃～300 seconds ℃.

13. the blow molding method of the synthetic resin described in claim 9 or 11, wherein, from parison contact with die surface to the time that blow molding pressure is full of moulded products inside fully be 1～5 second, with this condition blow molding.

14. the forming method of the synthetic resin of claim 1,2,3,9 or 11 described in each, wherein, heat insulation layer and metal level are with the driving fit of micro concavo-convex interface.

15. the forming method of the synthetic resin of claim 1,2,3,9 or 11 described in each, wherein, the heat resistant polymer that forms heat insulation layer is made of straight chain polymer amount polyimides.

16. the forming method of the synthetic resin of claim 1,2,3,9 or 11 described in each, wherein, use a kind of like this mould of coated metal layer, promptly, form the heat insulation layer outermost layer with the heat resistant polymer that has added micronized etching auxiliary agent by 1～30 weight %, then, this heat insulation layer outermost layer is carried out chemical etching to be handled, form the micro concavo-convex shape, carry out chemical plating in its surface, carry out once above chemical plating and/or plating more as required, form metal level, the closing force of this metal level is more than the 0.3kg/10mm.

17. the forming method of the synthetic resin of claim 1,2,3,9 or 11 described in each wherein, uses layer on surface of metal or the part metals laminar surface mould as mirror-like.

18. the forming method of the synthetic resin of claim 1,2,3,9 or 11 described in each wherein, uses layer on surface of metal or part metals laminar surface to be the concavo-convex mould of lens sample.

19. the forming method of the synthetic resin of claim 1,2,3,9 or 11 described in each wherein, uses layer on surface of metal or the part metals laminar surface delustring shape mould as micro concavo-convex.

20. the forming method of the synthetic resin of claim 1,2 or 3 described in each wherein, uses either party in the protuberance of layer on surface of metal and the recess to be mirror-like, the opposing party mould as the delustring shape.

21. the forming method of the synthetic resin of claim 1,2,3,9 or 11 described in each, wherein, the synthetic resin of moulding is the styrene resin that is selected from down group: polystyrene, polystyrene rubber reinforcement, SAN, ABS resin, styrene-methylmethacrylate copolymer; Be selected from the methacrylate resin in polymethyl methacrylate, the rubber enhancing polymethyl methacrylate; Merlon as non-crystalline resin.

22. the forming method of the synthetic resin of claim 1,2 or 3 described in each, wherein, synthetic resin is to contain that 5～65 weight % are fibrous, the synthetic resin of pulverous inorganic filling material, uses the hardness mould identical or higher with the hardness of inorganic filling material in the synthetic resin of mould outermost metal layer.

23. the forming method of the synthetic resin of claim 1,2 or 3 described in each, wherein, synthetic resin contains 20 weight %～65 weight % inorganic filling materials.