CN107636099A - Adhesive film, layered product and decorated profile body - Google Patents

Adhesive film, layered product and decorated profile body Download PDF

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Publication number
CN107636099A
CN107636099A CN201680033342.0A CN201680033342A CN107636099A CN 107636099 A CN107636099 A CN 107636099A CN 201680033342 A CN201680033342 A CN 201680033342A CN 107636099 A CN107636099 A CN 107636099A
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CN
China
Prior art keywords
layer
adhering agent
agent layer
adhesive film
layered product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201680033342.0A
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Chinese (zh)
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CN107636099B (en
Inventor
太田喜宽
锦织义治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
New Oji Paper Co Ltd
Oji Holdings Corp
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Oji Paper Co Ltd
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Publication date
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Publication of CN107636099A publication Critical patent/CN107636099A/en
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Publication of CN107636099B publication Critical patent/CN107636099B/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/12—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor of articles having inserts or reinforcements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

The present invention provides one kind when carrying out TOM shapings, the adhesive film that the foaming from adhering agent layer is inhibited.More particularly it relates to a kind of adhesive film, it is characterised in that there is adhering agent layer and be laminated in the decorative layer of a surface side of adhering agent layer, and volatile materials contained in adhering agent layer is less than 50ppm.

Description

Adhesive film, layered product and decorated profile body
Technical field
The present invention relates to a kind of adhesive film, layered product and decorated profile body.
The application is by claims priority based on the Japanese patent application submitted on June 15th, 2015 the 2015-120042nd Power, and its content is incorporated herein.
Background technology
Since in the past, part is filled to automobile interior exterior, household electrical appliances are protected or decorated with the surface of part etc. with part, building materials (decorative) when, after being processed by injection moulding or vacuum forming etc. to formed body, using spraying etc. in formed body Surface on be coated with coating, and be dried and be heating and curing.However, except there is the row of volatile organic solvent in this application Beyond the problem of operating environment of sening as an envoy to deteriorates, due to needing the flow chart of each profiled part and production equipment and needing weight Overcoating cloth coating, therefore the problem of the yield rate that coating be present is poor, productivity ratio is low.
In recent years, by automobile interior exterior dress part, household electrical appliances part, building materials part etc. lightweight for the purpose of, as into The use of the resin-formed body of type body develops.In the decoration (decorative) of resin-formed body, be not suitable for the feelings of spraying Condition is more, and various methods have been developed for the surface of decorated resin formed body.Wherein, the most table of decorating film decorated profile body is utilized Face and the method for obtaining decorated profile body, compared to the method for being coated or printing to surface using coating etc., there is design The free degree is high, the advantages of productivity ratio is also excellent.Further, since having used the trailing of decorating film can also decorate with three Concavo-convex formed body surface is tieed up, therefore is used in various uses.
As using method of the decorating film decoration with three-dimensional concavo-convex formed body surface, have it is three-dimensional it is overmolded (TOM into Type) method (patent document 1).TOM is shaped under vacuum or the forming method under reduced pressure, and it is by decorating film Crimped with formed body and obtain the method for decorated profile body.In TOM shapings, no matter how the material of formed body can enter luggage Decorations.In addition, without setting vacuum hole in formed body, back taper portion, end entrainment portion can be carried out overmolded.
In decorating film used in TOM shapings, exist and the viscous of adhesive phase or adhering agent layer has been laminated on decorative layer Film etc..When obtaining decorated profile body using the film with decorative layer and adhesive phase, heating when being molded by TOM is used And the adhesive of cohesive can be obtained, so as to attach decorative layer on adherend.In addition, using has decorative layer and adhering agent layer Adhesive film when, using the adhesion strength of adhering agent layer, make adhesive film and formed body adherence.
For forming the sticker of adhering agent layer, usually using solvent sticker, but also to ultraviolet curing The use of type adhesive is studied.Such as glued Patent Document 2 discloses one kind with decorative layer with ionizing radiation curable The cosmetic sheet of mixture layer.Herein, ionizing radiation curable adhesive phase has the property for the temporary adhesion that can carry out certain time Matter, and form adhesive monomer component polymerisation be time dependent carry out.
Prior art literature
Patent document
Patent document 1：No. 3733564 publications of Japanese Patent No.
Patent document 2：Japanese Unexamined Patent Publication 2004-142107 publications
The content of the invention
The technical problem to be solved in the present invention
As described above, when the adhesive film with decorative layer and adhering agent layer is used as into decorating film, make in adhering agent layer Situation with solvent sticker is more.However, during using solvent sticker, adhering agent layer easily bubbles, and becomes problem.
In addition, in patent document 2, for being studied in adhering agent layer using ultraviolet-curing adhesive, but Learnt by the research of the present inventor, when the decorating film of patent document 2 is used in into TOM shapings, glued temporarily Easily bubbled after conjunction, deteriorate yield rate of decorated profile body etc..
Therefore, the present inventor is being carried out to solve the technical problem of such prior art with providing one kind When TOM is molded, studied for the purpose of the adhesive film that the foaming from adhering agent layer is inhibited.
Solves the technological means of technical problem
The present inventor has made intensive studies to solve above-mentioned technical problem, as a result finds, with dress Adorn in the adhesive film of layer and adhering agent layer, it is certain following by the way that volatile ingredient contained in adhering agent layer is set in, can Suppress to carry out foaming during TOM shapings.
Specifically, the present invention has following structure.
[1] a kind of adhesive film, it is characterised in that there is adhering agent layer and be laminated in the decoration of a surface side of adhering agent layer Layer, contained volatile materials is less than 50ppm in adhering agent layer.
[2] adhesive film according to [1], wherein, the sticker for forming adhering agent layer is ultraviolet hardening sticker.
[3] according to the adhesive film described in [1] or [2], wherein, volatile materials is selected from as the viscous of composition adhering agent layer The monomer of the constituent of agent and as at least one kind of in the oligomer of the constituent for the sticker for forming adhering agent layer.
[4] adhesive film according to any one of [1]~[3], wherein, the sticker for forming adhering agent layer contains (first Base) acrylate monomeric units.
[5] adhesive film according to any one of [1]~[4], wherein, the thickness of adhering agent layer is more than 20 μm.
[6] adhesive film according to any one of [1]~[5], wherein, the thickness of decorative layer is more than 75 μm.
[7] adhesive film according to any one of [1]~[6], it is used under vacuum condition or under reduced pressure Shaping.
[8] a kind of layered product, it has：Adhering agent layer, be laminated in adhering agent layer a surface side decorative layer and stacking Separation layer in another surface side of adhering agent layer, another surface side are a surface side opposite with being laminated with the face of decorative layer；Its It is characterised by, contained volatile materials is less than 50ppm in adhering agent layer.
[9] according to the layered product described in [8], wherein, in adhering agent layer, decorative layer and separation layer at least any one have Sheet resistance is 1 × 105~1 × 1012Ω/ layer.
[10] layered product according to [8] or [9], wherein, it is 1 × 10 that separation layer, which has sheet resistance,5~1 × 1012 Ω/ layer.
[11] a kind of decorated profile body, it is contained the adhesive film any one of [1]~[7] and entered using adhesive film The formed body of luggage decorations.
[12] a kind of manufacture method of decorated profile body, it includes：Under vacuum or under reduced pressure, by adhesive film The process being laminated on formed body；Using draught head, process adhesive film being crimped on formed body；Adhesive film has sticker Layer and the decorative layer for the surface side for being laminated in adhering agent layer, and volatile materials contained in adhering agent layer is less than 50ppm.
Invention effect
In accordance with the invention it is possible to obtain when carrying out TOM shapings, the adhesion that the foaming from adhering agent layer is inhibited Film.Therefore, if using the adhesive film of the present invention, the productivity ratio of decorated profile body can be improved, and it is excellent to obtain design Different decorated profile body.
Brief description of the drawings
Fig. 1 is the sectional view of an example of the structure for representing the adhesive film of the present invention.
The sectional view of the structure of the layered products of Fig. 2 to illustrate the invention.
The sectional view of the structure of the decorated profile bodies of Fig. 3 to illustrate the invention.
Fig. 4 is the figure for illustrating the formed body used in embodiment and comparative example.Fig. 4 (a) is top view, and Fig. 4 (b) is the right side Side view, Fig. 4 (c) are upward view.
Embodiment
Hereinafter, the present invention is described in detail.Below in the explanation of described constitutive requirements, generation is based on although existing Table embodiment and concrete example and situation about illustrating, but the present invention is not limited by such embodiment.In addition, The number range represented by "~" is used to refer to using numerical value described before and after "~" as lower limit and the upper limit in this specification Value and comprising scope.
(adhesive film)
The adhesive film of the present invention has adhering agent layer and is laminated in the decorative layer of a surface side of adhering agent layer.In adhering agent layer Contained volatile materials is less than 50ppm.Contained volatile materials is preferably smaller than 30ppm in adhering agent layer, more preferably Below 15ppm, particularly preferably below 5ppm.Herein, volatile materials refers to what is volatilized under 150 DEG C of vacuum condition Material.In addition, the adhesive film of the present invention refers to fit in the film by before the TOM shapings on viscous object (formed body), for this hair For bright, it is characterised in that in the adhesive film before fitting, the containing ratio of volatile materials is within the above range.
As volatile materials, such as can include, selected from solvent, as form adhering agent layer sticker composition into Point monomer and as composition adhering agent layer sticker constituent oligomer in it is at least one kind of.In addition, as viscous The oligomer for the constituent of agent is the oligomer being polymerized using 2~5 as the monomer of the constituent of sticker.
Because the adhesive film of the present invention has said structure, therefore when being molded under vacuum or under reduced pressure (when TOM is molded), can suppress the foaming in adhering agent layer.Further, since the adhesive film of the present invention can be to as by viscous pair The formed body of elephant plays excellent adhesion strength, therefore is preferably used as the adhesion of the shaping under vacuum condition or under reduced pressure Film.
Fig. 1 is the sectional view of an example of the structure for representing the adhesive film of the present invention.As shown in figure 1, the present invention's is viscous Film 20 with decorative layer 22 and adhering agent layer 24.Adhering agent layer 24 is laminated in a surface side of decorative layer 22.In such adhesion In film 20, adhering agent layer 24 is used as by the surface of the formed body of viscous object by being pasted on, so as to decorated profile body.
In the adhesive film of the present invention, the thickness of adhering agent layer is preferably more than 20 μm, more preferably more than 35 μm, more enters one Step is preferably more than 70 μm, particularly preferably more than 150 μm.It is above-mentioned by the way that the thickness of adhering agent layer is set in the present invention In the range of, in the case that adhering agent layer bites foreign matter, it can also suppress foreign matter shape emersion to the table of decorated profile body Face.Therefore, if small foreign matter or bubble, even if then also unaffected in the case where biting.
In addition, the thickness of decorative layer is preferably more than 50 μm, more preferably more than 100 μm, more preferably 180 μm with On.In the present invention, by the way that within the above range, the thickness setting of decorative layer is bitten into the situation of foreign matter even in adhering agent layer Under, it can also suppress foreign matter shape emersion to the surface of decorated profile body.
(adhering agent layer)
The sticker for forming adhering agent layer is preferably ultraviolet hardening sticker (UV curing types sticker), more preferably Acrylic compounds ultraviolet hardening sticker.It as ultraviolet hardening sticker, such as can include, contain acrylic compounds list The no-solvent type sticker of body and/or acrylic compounds oligomer and Photoepolymerizationinitiater initiater.
The sticker for forming adhering agent layer preferably comprises (methyl) acrylate monomeric units as composition acrylic polymer The unit of compound.Herein, " unit " refers to the repeat unit (monomeric unit) for forming polymer.In addition, " (methyl) acrylic acid " Mean comprising both " acrylic acid " and " methacrylic acid ".
As (methyl) acrylate monomer, for example, can include (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (first Base) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid-2-ethyl oneself Ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, the different nonyl of (methyl) acrylic acid Ester, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) acrylic acid n-undecane base ester, (methyl) propylene Sour lauryl, (methyl) acrylic acid n-dodecane base ester, (methyl) stearyl acrylate base ester, (methyl) acrylic acid iso stearyl Ester, (methyl) isobornyl acrylate, (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate, (methyl) Cyclohexyl acrylate, (methyl) benzyl acrylate etc..These (methyl) acrylate monomers can be used alone, and also may be used To use two or more simultaneously.
Wherein, preferably using selected from (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) i-butyl It is at least one kind of in ester, (methyl) acrylic acid-2-ethyl caproite.
In addition, it can also contain following compositions as needed.Such as ethylene glycol two (methyl) acrylate, three second can be included Glycol two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate, 1, 9- nonanediols two (methyl) acrylate, 1,6 hexanediol diacrylate, polytetramethylene glycol two (methyl) acrylate, new penta 2 Alcohol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol Two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, Ji Wusi Alcohol four (methyl) acrylate etc..It can further include：It is composition with carboxyl, preferably acrylic acid, methacrylic acid, suitable Butene dioic acid, crotonic acid, β-propyloic acrylic ester；And/or there is the composition of hydroxyl, preferably 2- ethoxys (methyl) propylene Acid esters, hydroxypropyl (methyl) acrylate, 2- hydroxyls butyl (methyl) acrylate, chloro- 2- ethoxys (methyl) acrylate, 4- Hydroxyl butyl (methyl) acrylate, 6- hydroxyls hexyl (methyl) acrylate, 8- hydroxyls octyl group (methyl) acrylate；And/or it can be total to Poly- unsaturated composition, preferably acrylamide, Methacrylamide, vinyl acetate, (methyl) acrylonitrile, macromolecular list Body.It is preferred that these compositions with carboxyl, the composition with hydroxyl and copolymerizable composition, with the 0.1 of acrylic polymer ~30 mass %, preferably with 1~10 mass % and by comprising.
The sticker for forming adhering agent layer preferably comprises the monomer enumerated as the unit for forming acrylic polymer And/or oligomer.Relative to the gross mass of adhering agent layer, monomer and/or oligomer are preferably 30~98 mass %, particularly preferably For 70~95 mass %.By the way that the blended amount of monomer and/or oligomer is set within the above range, easily by the viscous of sticker Degree regulation can form adhering agent layer to required scope by coating.
In addition, the sticker of adhering agent layer is formed, in addition to containing acrylic polymer, it also may be preferable in sticker In aliphatic (C5) the class Petropols containing 0~40 mass %, further preferably 10~25 mass %, aromatic series (C9) class stone Oleoresin, copolymerization (C5/C9) class Petropols, bicyclopentadiene (DCPD) class Petropols, coumarone-indene resin, containing α- The styrene resin of methyl styrene resinoid, rosin, rosin ester resin, terpenoid resin, aromatic modified terpene resin, Terpene-phenolic resin and their hydrogenation type resin etc..
The sticker of adhering agent layer is formed, preferably comprises the poly- of 0.1~10 mass %, further preferably 0.5~5 mass % Close initiator.Polymerization initiator is preferably Photoepolymerizationinitiater initiater.As polymerization initiator, such as acetophenones initiation can be included Agent, benzoin ethers initiator, benzophenone initiator, hydroxyalkyl phenones class initiator, thioxanthene ketone class initiator, amine draw Send out agent, acylphosphine oxide class initiator etc..
As acetophenones initiator, diethoxy acetophenone, benzil dimethyl ketal etc. can be specifically included.
As benzoin ethers initiator, benzoin, benzoin methylether etc. can be specifically included.
As benzophenone initiator, benzophenone, methyl o-benzoylbenzoate etc. can be specifically included.
As hydroxyalkyl phenones class initiator, can specifically include 1- hydroxy-cyclohexyl-phenyls -one, 2- hydroxyls- 2- methyl isophthalic acids-phenyl-propan -1- ketone etc..
As thioxanthene ketone class initiator, ITX, 2,4- dimethyl thioxanthones etc. can be specifically included.
As amine initiator, triethanolamine, 4- mesitylenic acid ethyl esters etc. can be specifically included.
As acylphosphine oxide class initiator, 2 can be specifically included, 4,6- trimethylbenzoyl-diphenyls-oxidation Phosphine, double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides etc..
, also can be as needed in adhering agent layer, containing known to conduct in the range of the effect of the present invention is not damaged The crosslinking agent of additive, chain-transferring agent, sensitizer, light stabilizer, filler, pigment, tackifier, viscous regulator, wetting agent, Levelling agent, defoamer, preservative, dispersant, antioxidant, antifreezing agent, fire retardant etc..
The mean molecule quantity for forming the acrylic polymer of adhering agent layer is preferably 10,000~5,000,000, more preferably 300,000 ~300 ten thousand, particularly preferably 700,000~2,500,000.By the way that the mean molecule quantity of acrylic polymer is set in into above range It is interior, when being molded (TOM shapings) under vacuum or under reduced pressure, it is possible to increase to the tracing ability of formed body, also can Enough decorate the formed body of complicated shape.In addition, the distribution (Mw/Mn) of the molecular weight of acrylic polymer is preferably 1~30, more Preferably 1~20, particularly preferably 1~6.In order to obtain the molecular weight distribution of target, what can be mixed with two or more is averaged The different polymer of molecular weight.
By the distribution for the molecular weight for expanding acrylic polymer, it is molded under vacuum or under reduced pressure When (TOM shapings), it is possible to increase to the tracing ability of formed body, can also decorate the formed body of complicated shape.
The sheet resistance of adhering agent layer is preferably 1 × 105~1 × 1012Ω/, more preferably 1 × 106~1 × 1012Ω/ □.Particularly separation layer described later sheet resistance not 1 × 105~1 × 1012In the case of in the range of Ω/, adhesion The sheet resistance of oxidant layer is preferably within the above range.In addition, the sheet resistance on adhering agent layer, as long as the surface electricity of any surface Resistance is within the above range.
In order to which the sheet resistance of adhering agent layer is set into 1 × 105~1 × 1012Ω/, adhering agent layer preferably comprise anti-quiet Electric agent.Particularly separation layer described later sheet resistance not 1 × 105~1 × 1012In the case of in the range of Ω/, glue Oxidant layer and preferably comprise antistatic additive.As the antistatic additive contained by adhering agent layer, can enumerate and separation layer institute described later energy The antistatic additive identical antistatic additive contained, preferable antistatic additive are also identical.
Furthermore it is possible to using Hiresta UX MCP-HT800 (Mitsubishi Chemical Analytech Co., Ltd. manufacture, mensuration mode：Apply constant voltage/leakage current (leakage current) mensuration mode) measure adhering agent layer Sheet resistance.
When adhering agent layer contains antistatic additive, relative to the gross mass of adhering agent layer, the content of antistatic additive is preferably 0.1~10 mass %, more preferably 0.5~7 mass %, more preferably 1~5 mass %.
It is preferably 10~200N/25mm according to the adhesion strengths determined of JIS Z 0237 as the adhesion strength of adhering agent layer, More preferably 25~100N/25mm.
(decorative layer)
The layered product of the present invention contains decorative layer.Decorative layer can be single layer structure, but be preferably to have to inhale containing ultraviolet Receive the sealer of agent and the layer of nonferrous layer.In addition, nonferrous layer preferably comprises pigment, dyestuff, metal, metal oxide etc.. Nonferrous layer can be containing pigment, dyestuff, metal, metal oxide resin bed, or by pigment, dyestuff, metal, gold Belong to oxide formed evaporation, sputtered layer, or can also be by containing pigment, dyestuff, metal, metal oxide ink layer It is printed on the layer formed on decorative layer.At this time it is also possible to the Printing Department is referred to as nonferrous layer (coloured portion).As printing now Method, it is not particularly limited, such as letterpress, hectographic printing, flexible printing, intaglio printing, ink jet printing can be included Deng.As the printing-ink used in these printings, the oil-based ink, Soybean Oil Ink, plant of Oxidation polymerization type can be included Thing oil ink, the UV ink of ultraviolet hardening, LED-UV ink, base gravure ink, flexible ink, ink for screen printing etc., it is especially excellent Select base gravure ink, ink for screen printing, jetted ink.As needed, can also be added in printing-ink pigment dispersing agent, defoamer, The additives such as ultra-violet absorber, antioxidant, antistatic additive, abrasion preventing agent, anti-blocking agent.
In addition, when nonferrous layer be containing pigment, dyestuff, metal, metal oxide resin bed when, resin bed is preferably by warm Plastic resin is formed.Specifically, preferably ABS resin (copolymer of acrylonitrile, butadiene and styrene), AS resin (propylene The copolymer of nitrile and styrene), it is AAS resin (copolymer of acrylonitrile, acrylic acid and styrene), acrylic resin, poly- to benzene Naphthalate, polybutylene terephthalate (PBT), nylon, polyacetals, polyphenylene oxide, phenol resin, urea resin, melamine Polyimide resin, liquid crystal polymer, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polysulfones, polyether sulfone, polyacetals, polyether-ether-ketone, polyphenylene sulfide Ether, PEI, polyamidoimide, makrolon, polyethylene, polypropylene, polystyrene, polyurethane resin, inclined dichloro Ethene, vinyl chloride etc..
The pigment that can have as nonferrous layer, inorganic pigment (alumina white, titanium oxide, zinc oxide, black oxidation can be included Iron, micaceous iron oxide, white lead, white carbon ink, strontium molybdate, carbon black, lead monoxide, lithopone, barite, cadmium red, cadmium mercury are red, iron Pellet, chrome vermillion, red lead, chrome yellow, cadmium yellow, baryta yellow, strontium yellow, titan yellow, titanium are black, chrome oxide green, cobalt oxide, cobalt green, turkey blue, ultramarine, Prussian blue, cobalt blue, cerulean blue, manganese violet, cobalt violet etc.) and organic pigment (shellac, insoluble azo colour, soluble azo face Material, condensed azo pigment, phthalocyanine blue, dyeing lake etc.)；Or toluidine red, everbright fast maroon, Chinese husky of common dye (Hansa Yellow), the insoluble azo colour such as benzidine yellow, pyrazolone red；Purplish red (the Helio of lithol red, Ai Liao Bordeaux), the soluble AZOpigments such as lithol fast scarlet nrh, permanent bordeaux 2B；The derivatives such as alizarin, indanthrone, thioindigoid maroons；Phthalocyanine The phthalocyanine pigments such as indigo plant, phthalocyanine green；The quinacridone-type pigments such as quinacridone is red, quinacridone magenta；It is red, scarlet etc. Class pigment；The isoindoline ketone pigment such as isoindolinone Huang, isoindolinone orange；Benzimidazolone yellow, benzimidazolone orange, Benzimidazolone is red to wait imidazolone pigment；The pyranthrone pigment such as pyranthrone is red, pyranthrone orange；Thioindigo class pigment；Condensation is even Nitrogen class pigment；Dione pyrrolo-pyrrole pigment；Yellow scholar's ketone yellow (flavanthrone yellow), amido yellow, quinophthalone be yellow, Other pigment such as nickel azophosphine, copper azomethine Huang, pyrene ketone orange, anthrone orange, the red, dioxazine violets of dianthracene quinone.The present invention is not by these The restriction of dyestuff, known any pigment can also be used.
The dyestuff that can have as nonferrous layer, can include acid dyes, basic-dyeable fibre, direct dyes, chemically-reactive dyes, Disperse dyes or food coloring etc..In addition, known any dyestuff can also be used in the present invention, and it is not limited.These dyestuffs In, the dyestuff of particularly preferred azo and phthalocyanines, in addition, particularly preferably acid dyes, direct dyes, chemically-reactive dyes, food With pigment etc..
The metal level that can have as nonferrous layer, aluminium, gold, silver, nickel, indium etc. can be included.
Sealer is the layer for the most surface for forming layered product, is also the layer for forming most surface in decorated profile body. Particularly when decorating the component of desired strength of automobile interior exterior dress part etc., it is desirable to sealer have be not easy scratch resistant and Intensity etc..The pencil hardness of the sealer of the present invention is preferably more than B, more preferably more than F.
Sealer is preferably resin bed.Specifically, ABS resin (acrylonitrile, butadiene and benzene are preferably included The copolymer of ethene), AS resins (copolymer of acrylonitrile and styrene), AAS resin (acrylonitrile, acrylic acid and styrene Copolymer), acrylic resin, polyethylene terephthalate, polybutylene terephthalate (PBT), nylon, polyacetals, polyphenyl Ether, phenol resin, urea resin, melmac, liquid crystal polymer, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polysulfones, polyethers It is sulfone, polyacetals, polyether-ether-ketone, polyphenylene sulfide, PEI, polyamidoimide, makrolon, polyethylene, polypropylene, poly- Styrene, polyurethane resin, vinylidene resin, vinyl chloride resin etc..Due to excellent scratch resistance, therefore more preferably propylene Acid resin.In addition, the sealer of the present invention can also be ionizing ray solidified resin.Ionizing ray solidified resin refers to lead to The resin crossed irradiating electron beam or ultraviolet etc. and solidified.In the present invention, ionizing ray solidified resin is preferably that essence is saturating It is bright.The ionizing ray solidified resin transparent as essence, such as preferably use acrylic compounds ultraviolet curable resin.
The sheet resistance of decorative layer is preferably 1 × 105~1 × 1012Ω/, more preferably 1 × 106~1 × 1012Ω/ □.Particularly in the sheet resistance of separation layer described later and above-mentioned adhering agent layer not 1 × 105~1 × 1012Ω/ model In the case of in enclosing, preferably the sheet resistance of decorative layer is within the above range.In addition, the sheet resistance on decorative layer, as long as The sheet resistance of any surface is within the above range.
, can be between sealer and nonferrous layer containing antistatic when the sheet resistance of decorative layer is set into above range Agent.Now, antistatic additive can use antistatic with antistatic additive identical cited in the project of separation layer described later Agent.
Furthermore it is possible to using Hiresta UX MCP-HT800 (Mitsubishi Chemical Analytech Co., Ltd. manufacture, mensuration mode：Apply constant voltage/leakage current mensuration mode) measure decorative layer sheet resistance.
(layered product)
The present invention relates to a kind of layered product, and it has：Adhering agent layer, be laminated in adhering agent layer a surface side decorative layer, And the separation layer of another surface side of adhering agent layer is laminated in, another surface side is opposite with being laminated with the face of decorative layer one Surface side.Herein, volatile materials contained in adhering agent layer is less than 50ppm.
Fig. 2 (a) is the sectional view of an example of the structure for representing the layered product of the present invention.As shown in Fig. 2 (a), this hair Bright layered product 30 has：Adhering agent layer 24, be laminated in adhering agent layer 24 a surface side decorative layer 22 and be laminated in adhesion The separation layer 26 of another surface side of oxidant layer 24, another surface side are a surface side opposite with being laminated with the face of decorative layer 22. Because layered product 30 has a separation layer 26, therefore in the keeping of layered product 30 etc., the foreign matters such as dirt can be suppressed and be attached to adhesion On the surface of oxidant layer 24.During using layered product 30 of the invention, the separation layer 26 is peeled off, exposes adhering agent layer 24.Then, glue Oxidant layer 24 to be glued on the formed body as adherend.In this specification, the layered product for having peeled separation layer 26 off is referred to as Adhesive film 20.
Fig. 2 (b) is the sectional view for the preferable structure for representing the layered product of the present invention.In the layered product 30 of the present invention, dress It is preferably the layer containing sealer 32 Yu nonferrous layer 34 to adorn layer 22.In addition, separation layer 26 is preferably containing substrate layer 42, stripping From oxidant layer 44 and the layer of antistatic layer 46.The layered product 30 of the present invention can have the layer in addition to above-mentioned layer, or dress Adoring layer 22 further has the structure of antistatic layer, and adhering agent layer has the structure of nonferrous layer and/or antistatic layer.
In addition, in the layered product 30 as shown in Fig. 2 (b), after separation layer 26 is peeled off, also as adhesive film 20.
The layered product of the present invention can be sheet due to structure as described above, can also be wound into volume Shape.During wound into rolls, preferably it is wound in a manner of separation layer is configured at mandrel side.
(separation layer)
The layered product of the present invention contains separation layer.Separation layer be preferably resin-made and not comprising paper base material layer.Pass through Using this separation layer, the foreign matters such as the dirt from paper are not had and are clamped between layered product and formed body, can effectively be pressed down Foreign matter processed bites.
The sheet resistance of separation layer is preferably 1 × 105~1 × 1012Ω/, more preferably 1 × 106~1 × 1012Ω/ □.In layered product, electrostatic interaction when peeling off separation layer being present and foreign matter is easily attached to inclining on adhering agent layer To.However, in the present invention, it is special by the way that within the above range, the sheet resistance setting of separation layer can be suppressed into the attachment of foreign matter It is not under vacuum or when being molded under reduced pressure (when TOM is molded), can more effectively suppresses biting for foreign matter. In addition, the sheet resistance on separation layer, as long as the sheet resistance of any surface is within the above range.
Separation layer is single layer structure, and the sheet resistance of the individual layer within the above range, but can be preferably isolated layer and have table The layer of surface resistance within the above range.Specifically, being preferably isolated layer has：Substrate layer, the surface side for being laminated in substrate layer Peeling agent layer and be laminated in substrate layer another surface side antistatic layer, another surface side be with being laminated with peeling agent layer The opposite surface side in face.Wherein, the sheet resistance of antistatic layer is preferably 1 × 105~1 × 1012Ω/□。
In the present invention, it is preferably isolated layer and contains antistatic additive, and the adhesive film being preferably made up of decorative layer and adhering agent layer In do not include antistatic additive.In the present invention, during using layered product, separation layer is peeled off from layered product, turn into by decorative layer with it is viscous The adhesive film of oxidant layer composition.Also, the adhesive film is glued on the formed body as adherend.That is, only separation layer contains During antistatic additive, antistatic additive is not just contained in decorated profile body, can further improve the overall durability of decorated profile body.
Furthermore it is possible to using Hiresta UX MCP-HT800 (Mitsubishi Chemical Analytech Co., Ltd. manufacture, mensuration mode：Apply constant voltage/leakage current mensuration mode) measure separation layer sheet resistance.
As shown in Fig. 2 (b), separation layer 26 is preferably the layer containing substrate layer 42, peeling agent layer 44 and antistatic layer 46, and It is preferred that antistatic layer 46 contains antistatic additive.Antistatic additive be preferably selected from ionic antistatic additive, organic antistatic additive and It is at least one kind of in inorganic antistatic additive, at least 1 more preferably in organic antistatic additive and inorganic antistatic additive Kind, particularly preferably inorganic antistatic additive.In addition, organic antistatic additive is more preferably pi-conjugated system electroconductive polymer Class antistatic additive.By using in pi-conjugated system electroconductive polymer class antistatic additive and inorganic antistatic additive extremely Few a kind is used as antistatic additive, can suppress the Humidity Dependence of antistatic property.That is, can be played in all humidity bands Antistatic property.Particularly inorganic antistatic additive, excellent antistatic property can be also played under low-humidity environment. Further, since ionic antistatic additive is relatively inexpensive, therefore it is capable of the manufacturing cost of inhibition layer stack.
, can although any known ionic antistatic additive can be used in the present invention as ionic antistatic additive It is preferred that include glyceric acid fatty acid ester, polyglyceryl fatty acid ester, sorbitan fatty ester, polyoxyethylene sorbitol Acid anhydride fatty acid ester, polyoxyethylene aliphatic alcohol ether, alkylsulfonate, alkylbenzenesulfonate, tetraalkylammonium salt, triakyl benzyl ammonium Salt, glyceryl monostearate, N, double (2- hydroxyethyls) alkylamines of N-, N, N- double (2- hydroxyethyls) alkylamide, polyoxy second The fatty acid ester of allylic alkylation amine, alkyl sulfate, alkylphosphonate, alkyl betaine, kayexalate, polyethylene glycol first Base acrylate copolymer, polyether ester amides etc..
As organic antistatic additive, preferably using pi-conjugated system electroconductive polymer class antistatic additive.As pi-conjugated System electroconductive polymer class antistatic additive, known arbitrary pi-conjugated system electric conductivity high score can also be used in of the invention Subclass antistatic additive, but preferably include polythiophene, polypyrrole, polyaniline etc., particularly preferably polythiophene.
Known arbitrary inorganic antistatic additive can also be used as inorganic antistatic additive, in the present invention, can be excellent Choosing includes ITO fillers, silver nanoparticle filler, oxidation antimony-doped tin oxide cladding titanium oxide etc., particularly preferably silver nanoparticle filler.
When antistatic layer contains antistatic additive, relative to the gross mass of antistatic layer, the content of antistatic additive is preferably 2 ~100 mass %, more preferably 50~100 mass %.In addition, the dried coating weight of antistatic layer be preferably 0.001~ 1g/m2, particularly preferably 0.01~0.2g/m2。
The substrate layer for forming separation layer is preferably resin bed, and resin bed is preferably made up of thermoplastic resin.Specifically, make For substrate layer, polyolefin film, polychloroethylene film, polyvinyl alcohol film, polyester film, polycarbonate membrane, polystyrene film can be included Or polyacrylonitrile film.Wherein, preferably using polyester film, particularly preferably using polyethylene terephthalate (PET) film.This Outside, substrate layer can also use the film through bumps processing such as lens coating, prism film, holographic film.
Peeling agent layer contains remover.As remover, the silicone of for example general add-on type or condensed type can be used Class remover.Particularly preferably using the high add-on type silicone remover of reactivity.As silicone remover, specifically may be used Include Dow Corning Toray Co., BY24-162, SD-7234 of Ltd manufactures etc., or Shin-Etsu Chemical Co., KS-3600, KS-774, X62-2600 of Ltd. manufactures etc..In addition, in silicone remover, preferably comprise with SiO2 Unit, (CH3)3SiO1/2Unit or CH2=CH (CH3)SiO1/2The silicone resin as organo-silicon compound of unit.As silicon The concrete example of ketone resin, Dow Corning Toray Co., BY24-843, SD-7292, SHR- of Ltd manufactures can be included 1404 etc., and KS-3800, X92-183 of the manufacture of Shin-EtsuChemical Co., Ltd.s etc..
The auxiliary additives such as catalyst, adhesion-imparting agent can be added into peeling agent layer.As catalyst, preferably enumerate Go out platinum class, the catalyst of tin class.In addition, as long as adhesion-imparting agent improves adherence, then arbitrary adhesion-imparting agent can be used, can be excellent Choosing includes silane coupler.
The dried coating weight of peeling agent layer is preferably 0.01~1g/m2, particularly preferably 0.05~0.2g/m2。
Separation layer can by being coated with substrate layer containing stripper solution and containing antistatic agent solution, and be dried and Formed.When being coated with each solution, size press coater (size press coater), door roll coater (gate can be used Roll coater), bar coater (bar coater), roll-coater, Kohler coater, knife type coater, rod-type knife type coater (rod blade coater), curtain coater (curtain coater), gravure coater etc..Wherein, preferably using once The double end coating machine of front and back is coated with, particularly preferably there is the intaglio process head (Gravure that can control less coating weight Head) and double end coating machine that front and back can be coated with.Thereby, it is possible to form work(simultaneously on the two sides of substrate layer Ergosphere, so as to improve the production efficiency of separation layer.
(manufacture method of layered product)
In the process of the layered product of the manufacture present invention, decoration is preferably being laminated in a manner of as structure as described above After layer, adhering agent layer and separation layer, irradiation light (ultraviolet or electron beam).In addition it is also possible in stacking separation layer, sticker After layer and separation layer, irradiation light (ultraviolet or electron beam), then it is bonded with decorative layer, so as to form said structure.When During to structured illumination light containing decorative layer, preferably from separation layer side irradiation light (ultraviolet or electron beam).
In the process of irradiation light (ultraviolet), preferably at least it is using the illumination of 200~400nm of wavelength scope 50mW/cm2Ultraviolet above is irradiated, and more preferably irradiates 70~3000mW/cm2Ultraviolet, particularly preferably irradiate 100 ~1000mW/cm2Ultraviolet.It is preferably 100~10000mJ/cm as accumulated light2, particularly preferably 300~3000mJ/ cm2.As the irradiator for carrying out this irradiation, preferably shone using selected from high-pressure mercury ultraviolet radiation device, metal halogen ultraviolet It is at least one kind of in emitter, electrodeless ultraviolet radiation device.By being 50mW/cm by the illumination of 200~400nm of wavelength scope2 Ultraviolet irradiation condition above is set as above range, can reduce the monomer component amount remained in adhering agent layer.In addition, By the way that irradiation condition is set as into above range, decorative layer can be suppressed and xanthochromia occur because of ultraviolet.
In the present invention, except the illumination of the scope using 200~400nm of wavelength is 50mW/cm2The photograph of ultraviolet above Penetrate beyond process, be 20mW/cm preferably using the illumination of 200~400nm of wavelength scope2Following ultraviolet is irradiated. It is 1~10mW/cm more preferably using the illumination of 200~400nm of wavelength scope2, particularly preferably the use of illumination is 2~5mW/cm2 Ultraviolet be irradiated.As the irradiator for carrying out this irradiation, preferably use in chemical lamp and/or black light at least 1 kind.By using these irradiators, preferably irradiate 0.01~30 minute, particularly preferably irradiate 0.1~20 minute, so as to tire out Product light quantity is preferably set to 10~1000mJ/cm2, more preferably it is set as 40~600mJ/cm2, particularly preferably it is set as 100~ 400mJ/cm2.By being 20mW/cm by the illumination of the scope using 200~400nm of wavelength2Following ultraviolet irradiation condition Above range is set to, the tracing ability of adhering agent layer can be improved when TOM is molded.
In the present invention, the illumination using 200~400nm of wavelength scope is 20mW/cm2Following ultraviolet is irradiated When, it is 50mW/cm preferably in the illumination of the scope using 200~400nm of wavelength2Before the process that ultraviolet above is irradiated Carry out.
In the present invention, by irradiating ultraviolet under conditions, as described above, can improve monomer the degree of polymerization while, The ratio of volatile materials contained in adhering agent layer is set to below setting.
(shaping (TOM shapings) under vacuum condition or under reduced pressure)
It is preferred that the layered product of the present invention is used in the shaping under vacuum condition or under reduced pressure.By using the present invention Layered product, when being molded under vacuum or under reduced pressure, can suppress the foreign matters such as dirt biting adhering agent layer Between formed body.Like this, pass through the shaping layered product of the present invention being used under vacuum condition or under reduced pressure, energy Enough play its effect.
In this specification, the shaping under vacuum condition or under reduced pressure refers to the shaping for being referred to as so-called TOM shapings Method.In TOM forming methods, including：Under vacuum or under reduced pressure, the work that adhesive film is laminated on formed body Sequence；And using draught head, process adhesive film being crimped on formed body.In addition, in this specification, under vacuum condition or subtract In shaping under the conditions of pressure, not using being provided with the formed body of vacuum hole in formed body, and make adhesive film and formed body The method of adherence.Specifically, the shaping under vacuum condition or under reduced pressure, can be by using Japanese Patent No. " vacuum forming device " described in No. 3733564 publications is carried out.
The present invention also relates to a kind of manufacture method of decorated profile body as described above.Specifically, decoration of the invention The manufacture method of formed body includes：Under vacuum or reduced pressure, the process that adhesive film is laminated on formed body；And pressing Under contracting air conditionses, using draught head, process adhesive film being crimped on formed body.In addition, the decorated profile body of the present invention Manufacture method in, preferably after the process that adhesive film is crimped on formed body, including the surface of layered product is heated to 100 ~180 DEG C of process.Now, preferably infrared heater is used in the heating on the surface of layered product.
In addition, the adhesive film used in the manufacture method of the decorated profile body of the present invention is above-mentioned adhesive film, adhesion Contained volatile materials is less than 50ppm in oxidant layer.
(decorated profile body)
The present invention also relates to a kind of decorated profile body, and it contains：By the decorative layer and sticker of layered product as described above The adhesive film of layer composition and the formed body decorated using adhesive film.Decorated profile body is that adhesive film is pasted on into shaping The material formed in the part or entire surface on the surface of body.That is, in decorated profile body, decorative layer layer via adhering agent layer It is folded.
Fig. 3 is the sectional view for the structure for illustrating decorated profile body 100.Fig. 3 represents to have decorated surface tool using adhesive film 20 There is the appearance after the formed body 50 of recess.As shown in figure 3, under vacuum or in the shaping under reduced pressure, even if not existing Vacuum hole is set in formed body 50, still can entrainment portion of overmolded back taper portion and end.No matter in addition, the material of product, It can be decorated.Thus, the formed body surface of the three-dimensional bumps with complexity can also be decorated, can be set The high decorated profile body 100 of meter property.
As formed body 50, metal material or the resins such as ED steel plates, Mg alloys, stainless steel (SUS), aluminium alloy can be included Formed body, but preferably resin-formed body.For instance, it may be preferable to use the ABS resin (copolymerization of acrylonitrile, butadiene and styrene Thing), AS resins (copolymer of acrylonitrile and styrene), AAS resin (copolymer of acrylonitrile, acrylic acid and styrene), third Olefin(e) acid resin, polyethylene terephthalate, polybutylene terephthalate (PBT), nylon, polyacetals, polyphenylene oxide, phenol resin, Urea resin, melmac, liquid crystal polymer, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polysulfones, polyether sulfone, polyacetals, It is polyether-ether-ketone, polyphenylene sulfide, PEI, polyamidoimide, makrolon, polyethylene, polypropylene, polystyrene, poly- Urethane resin, vinylidene resin, vinyl chloride resin etc..These resins can also be blended.For instance, it may be preferable to exemplify containing poly- Carbonate resin etc.., can be particularly preferably using being blended with makrolon and poly terephthalic acid fourth as containing polycarbonate resin The resin (PCPBT) of diol ester, the resin (PCABS) for being blended with makrolon and ABS resin, be blended with makrolon with PET resin (PCPET) etc..In addition, as vistanex, polypropylene (PP) can be particularly preferably used.
Specifically, ABS resin (copolymer of acrylonitrile, butadiene and styrene), AS resins (third are preferably included The copolymer of alkene nitrile and styrene), AAS resin (copolymer of acrylonitrile, acrylic acid and styrene), acrylic resin, poly- pair PET, polybutylene terephthalate (PBT), nylon, polyacetals, polyphenylene oxide, phenol resin, urea resin, trimerization Melamine resin, liquid crystal polymer, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polysulfones, polyether sulfone, polyacetals, polyether-ether-ketone, polyphenyl Thioether, PEI, polyamidoimide, makrolon, polyethylene, polypropylene, polystyrene, polyurethane resin etc..
It can be used in by the decorated profile body obtained by the present invention for example, automotive part is (for example, vehicle body, insurance The parts such as thick stick, spoiler, mirror, wheel, built-in material, and the part of various materials), motorcycle part, road Load materials (for example, traffic mark, soundproof wall etc.), tunnel material (for example, sidewall paneling etc.), rolling stock, furniture, musical instrument, household electrical appliances production Product, construction material, container, office appliance, sporting goods, toy etc..
Embodiment
Embodiment and comparative example is exemplified below out the feature of the present invention is described in further detail.Following implementation Material, usage amount, ratio, process content, processing sequence shown in example etc., can then be fitted without departing from spirit of the invention Work as change.Therefore, the scope of the present invention should not come being defined property be explained by concrete example as shown below.
(embodiment 1)
The ＞ of ＜ decorative layers 1
In acrylic film, (Mitsubishi Rayon Co., Ltd.s manufacture, ACRYPLEN HBA001P, and pencil hardness is 2H, thickness be 125 μm) one side on, using intaglio press by thickness turn into 5 μm in a manner of black ink is set in entire surface (DIC CORPORATION are manufactured, TRC1268) layer (nonferrous layer), has obtained decorative layer 1.
The ＞ of ＜ separation layers 1
PET that thickness is 38 μm (Toray Industries, Inc. manufacture,T60 one side) On, 0.07g/m is turned into dried coating weight2Mode, coating contain pi-conjugated system organic conductive material：It is poly- that (3,4- is sub- Ethylenedioxy thiophene) DENATRON P-502S (Nagase ChemteX Corporation manufactures), using drying machine with 130 DEG C of processing for having carried out 30 seconds.It thus form antistatic layer.
Then, on opposing sides, 0.1g/m is turned into dried weight2Mode, be coated with by thermohardening type silicone (Dow Corning Toray Co., Ltd.s manufacture, LTC300B) 100 mass parts, catalyst (Dow Corning Toray Co., Ltd. manufacture, SRX212) 1 mass parts composition remover, so as to form peeling agent layer.Then, using drying machine with 130 DEG C of processing for carrying out 60 seconds, have obtained separation layer 1.
The ＞ of ＜ stickers 1
Into the reaction vessel of nitrogen atmosphere, the mass parts of acrylic acid-2-ethyl caproite 95, the mass parts of acrylic acid 5 are added, are made Polymerisation is carried out with initiator (2,2'- azos are double (4- methoxyl groups -2,4- methyl pentane nitrile)) 0.01 mass parts, is gathered The sticker 1 that compound concentration is 9%, weight average molecular weight Mw is 1,500,000.
The ＞ of ＜ layered products 1
Into the sticker 1 of 100 mass parts, addition hexanediyl ester 0.1 mass parts, benzil dimethyl ketal 1 mass parts, punching sweeps nitrogen so as to remove the molten oxygen deposited completely, in the peeling agent layer side of separation layer 1 and 130 μm of decorative layer 1 Ink layer side between, by the thickness of adhering agent layer turn into 50 μm in a manner of be coated with (wet type lamination) sticker 1.Then, make With chemical lamp, 4mW/cm is turned into the illumination of wavelength 365nm ultraviolet2, accumulated light turn into 300mJ/cm2Mode, from every The side of absciss layer 1 is irradiated, and followed by high-pressure sodium lamp, turns into 100mW/cm with the illumination of wavelength 365nm ultraviolet2, accumulation Light quantity turns into 2000mJ/cm2Mode be irradiated, obtained layered product 1.Layered product is determined by gas chromatography Contained volatile materials in 1 adhering agent layer, its result is 5ppm.
The manufacture method ＞ of ＜ decorated profile bodies
Separation layer 1 is peeled off from layered product 1, forms adhesive film 1.The adhesive film 1 is installed on TOM forming machines.Will (Panasonic Corporation are manufactured inlet wire rain cover, production code member：WP9171) with outer surface (convex surface) side of the cover with The adhering agent layer of above-mentioned adhesive film 1 is installed on TOM forming machines (Fu-se Vacuum Forming Ltd. in relative in a manner of Manufacture, NGF forming machines) on.Adhesive film 1 is laminated on above-mentioned formed body with 130 DEG C by using TOM forming machines, thus Decorated profile body 1 is arrived.10 decorated profile bodies 1 have been manufactured in an identical manner.
In addition, the shape of above-mentioned inlet wire rain cover is shown in Fig. 4 (a)~(c).When viewed from above shown in such as Fig. 4 (a) During inlet wire rain cover shown in Fig. 4 (a)~(c), the length in length (longitudinal axis) direction is 90mm, the length in width (transverse axis) direction Spend for 60mm.
(embodiment 2)
Except the thickness of adhering agent layer 1 is set into 75 μm, separation layer 1 is changed to separation layer 2, and ultraviolet irradiation is set To be set to 300mW/cm merely with high-pressure sodium lamp, by the illumination of wavelength 365nm ultraviolet2, accumulated light be set to 3000mJ/cm2 Condition obtained beyond layered product 2, obtained decorated profile body 2 in the same manner as example 1.Determine adhering agent layer In contained volatile materials, its result is 23ppm.
The ＞ of ＜ separation layers 2
PET that thickness is 50 μm (Toray Industries, Inc. manufacture,T60 one side) On, 0.15g/m is turned into dried coating weight2Mode, be coated with glyceryl monostearate, entered using drying machine with 130 DEG C The processing of 30 seconds is gone.It thus form antistatic layer.
Then, on opposing sides, 0.1g/m is turned into dried weight2Mode, be coated with by thermohardening type silicone (Dow Corning Toray Co., Ltd.s manufacture, LTC300B) 100 mass parts and catalyst (Dow Corning Toray Co., Ltd. manufacture, SRX212) 1 mass parts composition remover, so as to form peeling agent layer.Then, using drying machine with 130 DEG C of processing for carrying out 60 seconds, have obtained separation layer 2.
(embodiment 3)
Except substituting sticker 1 with sticker 3 adhering agent layer 3, and useization are formed in a manner of thickness is 25 μm Lamp is learned, 4mW/cm is turned into the illumination of wavelength 365nm ultraviolet2, accumulated light turn into 100mJ/cm2Mode from separation layer 2 Side is irradiated, and followed by high-pressure sodium lamp, turns into 100mW/cm with the illumination of wavelength 365nm ultraviolet2, accumulated light into For 2000mJ/cm2Mode be irradiated, obtained beyond layered product 3, decorated in the same way as in example 2 Formed body 3.Volatile materials contained in the adhering agent layer of layered product 3 is determined, its result is 3ppm.
The ＞ of ＜ stickers 3
Into the reaction vessel of nitrogen atmosphere, add acrylic acid-2-ethyl caproite 90 mass parts, the mass parts of acrylic acid 5 and The mass parts of isobornyl acrylate 5, use initiator (2,2'- azos are double (4- methoxyl groups -2,4- methyl pentane nitrile)) 0.01 matter Measure part and carry out polymerisation, obtain the sticker 3 that polymer concentration is 8%, weight average molecular weight Mw is 2,000,000.
(embodiment 4)
Substitute sticker 1 with sticker 4 and form adhering agent layer 4, and substitute decorative layer 1 using separation layer 3, in addition, sharp Substitute high-pressure sodium lamp with metal halid lamp, 100mW/cm is turned into the illumination of wavelength 365nm ultraviolet2, accumulated light turns into 2000mJ/cm2Mode be irradiated, so as to manufacture the structure of the separation layer 3 of 1/ adhering agent layer of separation layer 4/, then peel isolation Layer 1, be bonded decorative layer 1 on the adhering agent layer 4 exposed so as to obtain layered product 4 using roller make-up machine, in addition, with The identical mode of embodiment 1 has obtained decorated profile body 4.Volatile materials contained in the adhering agent layer of layered product 4 is determined, Its result is 14ppm.
The ＞ of ＜ stickers 4
Into the reaction vessel of nitrogen atmosphere, the mass parts of butyl acrylate 95, the mass of acrylic acid -2- hydroxy methyls 5 are added Part, polymerisation is carried out using initiator (2,2'- azos are double (4- methoxyl groups -2,4- methyl pentane nitrile)) 0.01 mass parts, is obtained The solution 4 that polymer concentration is 11%, weight average molecular weight Mw is 1,000,000 is arrived.Rosin tackifier are added into the solution 4 (Arakawa Chemical Industries, Ltd. manufactures, KE311) 15 mass parts, are stirred, have obtained sticker 4.
The ＞ of ＜ separation layers 3
By nano silver wire (Cold stones are manufactured, CST-NW-S40) and polyesters binding agent (TAKAMATSU OIL＆ FAT CO., LTD manufactures, PESRESIN A-645GH), turn into 20 with dried weight:80 mode is blended, and is applied Be distributed in PET that thickness is 50 μm (Toray Industries, Inc. manufacture,T60 on one side).With dry Coating weight after dry turns into 0.01g/m2Mode set coating weight, and be coated with dust free room (1000 grades).Then, Using drying machine with 130 DEG C of processing for carrying out 30 seconds, antistatic layer D is formd.
Then, in dust free room (1000 grades), 0.1g/m is turned into dried weight2Mode, will be by thermohardening type Silicone (Dow Corning Toray Co., Ltd.s manufacture, LTC300B) 100 mass and catalyst (Dow Corning Toray Co., Ltd. manufacture, SRX212) 1 mass parts composition remover be coated on opposing face, form peeling agent layer.Then, it is sharp With drying machine with 130 DEG C of processing for carrying out 60 seconds, separation layer 3 has been obtained.
(embodiment 5)
Except with sticker 5 substitute sticker 1, the thickness of adhering agent layer 5 is set to beyond 25 μm, with the phase of embodiment 4 Same mode manufactures layered product 5, has obtained decorated profile body 5.
Volatile materials contained in the adhering agent layer of layered product 5 is determined, its result is 4ppm.
The ＞ of ＜ stickers 5
Into the reaction vessel of nitrogen atmosphere, the mass parts of acrylic acid-2-ethyl caproite 90, the mass parts of acrylic acid 10 are added, Polymerisation is carried out using initiator (2,2'- azos are double (4- methoxyl groups -2,4- methyl pentane nitrile)) 0.01 mass parts, is obtained The solution 5 that polymer concentration is 11%, weight average molecular weight Mw is 1,500,000.Terpenes tackifier are added into the solution 5 (YASUHARA CHEMICAL CO., LTD. manufactures, TH130) 10 mass parts and aliphatic hydrocarbon tackifier (ArakawaChemical Industries, Ltd. manufactures, ARKON M100), is stirred, has obtained sticker 5.
(embodiment 6)
Except the thickness of adhering agent layer is set into 200 μm, and substituted with separation layer 4 beyond separation layer 2, with embodiment 2 Identical mode manufactures layered product 6, has obtained decorated profile body 6.Determine volatility contained in the adhering agent layer of layered product 6 Material, its result are 30ppm.
The ＞ of ＜ separation layers 4
PET that thickness is 38 μm (Toray Industries, Inc. manufacture,T60 one side) On, 0.1g/m is turned into dried weight2Mode, be coated with by thermohardening type silicone (Dow Corning Toray Co., Ltd. manufacture, LTC300B) 100 mass parts, catalyst (Dow Corning Toray Co., Ltd.s manufacture, SRX212) 1 mass The remover of part composition, so as to form peeling agent layer.Then, obtained using drying machine with 130 DEG C of processing for carrying out 60 seconds Separation layer 4.
(comparative example 1)
Though being intended to obtain decorated profile body 11 using the adhesive film 11 for having peeled off separation layer 4 from layered product 11, work as When being processed using TOM forming machines with 130 DEG C, adhering agent layer bubbles, and fails to obtain good decorated profile body.Measure Contained volatile materials in the adhering agent layer of layered product 11, its result is 80ppm.
The ＞ of ＜ layered products 11
On the peeling agent layer of separation layer 4, sticker 11 is coated with a manner of dried thickness turns into 25 μm, and 90 After drying in 10 minutes has been carried out at DEG C, decorative layer 1 is bonded using roller make-up machine, so as to obtain layered product 11.
The ＞ of ＜ stickers 11
By the mass parts of butyl acrylate 65, the mass parts of methyl acrylate 30 and the mass parts of acrylic acid 5 input nitrogen atmosphere In reaction vessel (being provided with temperature controller, mixer, return channel), the mass parts of ethyl acetate 200 and azodiisobutyronitrile are added 0.1 mass parts, polymerisation is carried out, has obtained polymer A.Resulting polymer A weight average molecular weight Mw is 800,000.By institute Obtained polymer A, poly alpha methylstyrene (molecular weight Mw=850,000, Tg=105 DEG C, Wako Pure Chemical Industries, Ltd. are manufactured) and crosslinking agent (MITSUBISHI GAS CHEMICAL COMPANY, INC. manufactures, TETRAD- X), 98 are turned into dry weight ratio:10:2 mode is blended, and has obtained sticker 11.
(comparative example 2)
Though being intended to obtain decorated profile body 12 using the adhesive film 12 for having peeled off separation layer 2 from layered product 12, work as When being processed using TOM forming machines with 130 DEG C, adhering agent layer bubbles, and fails to obtain good decorated profile body.Measure Contained volatile materials in the adhering agent layer of layered product 12, its result is 140ppm.
The ＞ of ＜ layered products 12
Except on the peeling agent layer of separation layer 2, be coated with a manner of dried thickness turns into 75 μm sticker 12 with Outside, layered product 12 has been obtained in a manner of with the identical of comparative example 1.
The ＞ of ＜ stickers 12
The mass parts of butyl acrylate 65, the mass parts of methyl acrylate 30 and the mass parts of 2-Hydroxy ethyl acrylate 5 are put into In the reaction vessel (being provided with temperature controller, mixer, return channel) of nitrogen atmosphere, the mass parts of ethyl acetate 200 and idol are added The mass parts of nitrogen bis-isobutyronitrile 0.1, polymerisation is carried out, has obtained polymer B.The weight average molecular weight Mw of resulting polymer B For 800,000.
By resulting polymer B, crosslinking agent (MITSUBISHI GAS CHEMICAL COMPANY, INC. manufacture, TETRAD-X) and double trifluoromethanesulfonimides, 96 are turned into dry weight ratio:2:2 mode is blended, and is adhered Agent 12.
(comparative example 3)
Though being intended to obtain decorated profile body 13 using the adhesive film 13 for having peeled off separation layer 1 from layered product 13, work as When being processed using TOM forming machines with 130 DEG C, adhering agent layer bubbles, and fails to obtain good decorated profile body.
The ＞ of ＜ layered products 13
Except using high-pressure sodium lamp, the illumination of wavelength 365nm ultraviolet is set into 100mW/cm2, accumulated light is set to 50mJ/cm2In addition, layered product 13 has been obtained in the same manner as example 1.Determine institute in the adhering agent layer of layered product 13 The volatile materials contained, its result are 610ppm.
(comparative example 4)
Though being intended to obtain decorated profile body 14 using the adhesive film 14 for having peeled off separation layer 1 from layered product 14, work as When being processed using TOM forming machines with 130 DEG C, adhering agent layer bubbles, and fails to obtain good decorated profile body.
The ＞ of ＜ layered products 14
Except using metal halid lamp, turning into 100mW/cm with the illumination of wavelength 365nm ultraviolet2, accumulated light into For 50mJ/cm2Mode be irradiated beyond, the adhering agent layer 4/ of separation layer 1/ is manufactured in a manner of same as Example 4 and is isolated The structure of layer 3, then peels separation layer 1, decorative layer 1 is bonded on the adhering agent layer 4 exposed so as to obtain using roller make-up machine Layered product 14.Volatile materials contained in the adhering agent layer of layered product 14 is determined, its result is 310ppm.
(evaluation)
(measure of sheet resistance value)
After damping placed 1 day in the environment of 23 DEG C, the 50%RH by layered product, Hiresta UX MCP-HT800 are utilized (Mitsubishi Chemical Analytech Co., Ltd. manufacture) determines sheet resistance.
(TOM mouldabilities)
During by being molded to the adhesive film of embodiment 1~6 and comparative example 1~4, the situation for not occurring bubbling is evaluated as Good forming ability (zero).It will find that the situation of foaming is evaluated as insufficient formability (×) when film is molded.Show the result in table 1.
(defect number)
Dress to having used the layered product (adhesive film) cured in the environment of 23 DEG C, relative humidity is 50% The surface of decorations formed body is observed, and superficial expansion is counted into number the defects of convex.Utilize laser microscope (VK- X100, KEYENCE Co., Ltd manufacture) observation in each embodiment and comparative example obtained by decorated profile body upper surface (region of the upper surface corresponded in Fig. 4 (a)), is considered as defect for more than 3 μm persons by height and its quantity is counted. In addition, defect number is the same zone of 10 decorated profile bodies manufactured in an identical manner respectively in each embodiment and each comparative example The defects of domain number average value.
(number of the defects of under low-humidity environment)
In the same way as described above, cured in the environment of 15 DEG C, relative humidity is 30% to having used The surface of decorated profile body of layered product (adhesive film) observed, defect number is counted, has obtained average value.
(adhesion strength)
25 × 50mm test film is attached on ABS plates, carries out crimping fitting (2kg rollers, 1 reciprocal) and heat treatment (130 DEG C, 1 minute), after placed 24 hours, using cupping machine, determine the stripping using peeling rate as 300mm/ minutes Be 180 degree from speed, peel angle, the condition that measurement temperature is 23 DEG C, measure humidity is 50% is when test film is peeled off, by it Peel required power.
(durability (grid test))
Decorated profile body is placed 500 hours in the environment of 80 DEG C, after placement at room temperature, on the surface of the film with 2mm interval is included in longitudinal and transverse 11 cuttings trace, so as to which 100 gridiron patterns be made.Show adhesive tape adherence in its table When another implication is peeled off after on face, unstripped and residual grid number.
[table 1]
When carrying out TOM shapings using adhesive film resulting in embodiment, TOM good forming abilities.On the other hand, using than When carrying out TOM shapings compared with adhesive film resulting in example, there is foaming from adhering agent layer.
In addition, the defects of layered product obtained by embodiment number it is few, good adhesion strength is played to formed body.Moreover, The excellent in te pins of durability of decorated profile body obtained by understanding in embodiment.
Description of reference numerals
20：Adhesive film；22：Decorative layer；24：Adhering agent layer；26：Separation layer；30：Layered product；32：Sealer；34： Nonferrous layer；42：Substrate layer；44：Peeling agent layer；46：Antistatic layer；50：Formed body；100：Decorated profile body.

Claims (12)

  1. A kind of 1. adhesive film, it is characterised in that there is adhering agent layer and be laminated in the decorative layer of a surface side of the adhering agent layer,
    Contained volatile materials is less than 50ppm in the adhering agent layer.
  2. 2. adhesive film according to claim 1, wherein, the sticker for forming the adhering agent layer glues for ultraviolet hardening Agent.
  3. 3. adhesive film according to claim 1 or 2, wherein, the volatile materials is selected from solvent, as described in composition The monomer of the constituent of the sticker of adhering agent layer and as the sticker for forming the adhering agent layer constituent it is low It is at least one kind of in polymers.
  4. 4. according to adhesive film according to any one of claims 1 to 3, wherein, the sticker for forming the adhering agent layer contains (methyl) acrylate monomeric units.
  5. 5. according to adhesive film according to any one of claims 1 to 4, wherein, the thickness of the adhering agent layer is more than 20 μm.
  6. 6. according to adhesive film according to any one of claims 1 to 5, wherein, the thickness of the decorative layer is more than 75 μm.
  7. 7. according to adhesive film according to any one of claims 1 to 6, its be used under vacuum condition or reduced pressure under Shaping.
  8. 8. a kind of layered product, it has：Adhering agent layer, be laminated in the adhering agent layer a surface side decorative layer and stacking Separation layer in another surface side of the adhering agent layer, another surface side are opposite with being laminated with the face of the decorative layer one Surface side；
    Characterized in that, volatile materials contained in the adhering agent layer is less than 50ppm.
  9. 9. layered product according to claim 8, wherein, in the adhering agent layer, the decorative layer and the separation layer It is 1 × 10 that at least any one, which has sheet resistance,5~1 × 1012Ω/ layer.
  10. 10. layered product according to claim 8 or claim 9, wherein, it is 1 × 10 that the separation layer, which has sheet resistance,5~1 × 1012Ω/ layer.
  11. 11. a kind of decorated profile body, it contains adhesive film according to any one of claims 1 to 7 and utilizes the adhesion The formed body that film is decorated.
  12. 12. a kind of manufacture method of decorated profile body, it includes：Under vacuum or under reduced pressure, adhesive film is laminated In the process on formed body,
    Using draught head, the adhesive film is crimped on the process on the formed body；
    The adhesive film has adhering agent layer and is laminated in the decorative layer of a surface side of the adhering agent layer, and the adhering agent layer In contained volatile materials be less than 50ppm.
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