WO2012090902A1 - 透明多層シートおよびその成形体 - Google Patents
透明多層シートおよびその成形体 Download PDFInfo
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- WO2012090902A1 WO2012090902A1 PCT/JP2011/080008 JP2011080008W WO2012090902A1 WO 2012090902 A1 WO2012090902 A1 WO 2012090902A1 JP 2011080008 W JP2011080008 W JP 2011080008W WO 2012090902 A1 WO2012090902 A1 WO 2012090902A1
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- multilayer sheet
- transparent multilayer
- less
- resin composition
- base material
- Prior art date
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- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- 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
- B29C51/10—Forming by pressure difference, e.g. vacuum
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- 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
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/006—Using vacuum
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- 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
- B29C51/14—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 using multilayered preforms or sheets
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31924—Including polyene monomers
Definitions
- the present invention relates to a transparent multilayer sheet and a molded body thereof, and more particularly to a transparent multilayer sheet and a molded body thereof used for applications such as vending machine display and decoration of industrial materials.
- a crystalline resin typified by polypropylene is opaque due to its high crystallinity (crystallinity, crystallization speed, spherulite size, etc.) in a normal film forming method.
- crystallinity crystallization speed, spherulite size, etc.
- a method of producing a large amount of fine crystals with a nucleating agent to suppress the growth of spherulites, a rapid cooling method using a belt process, and the like are employed.
- Patent Document 1 a method for producing a sheet made of a composition containing homopolypropylene and a nucleating agent by a rapid cooling method using a belt process has been proposed (see Patent Document 1).
- a sheet made of a composition containing homopolypropylene, petroleum resin, and a dibenzylidene sorbitol derivative as a nucleating agent has been proposed (see Patent Document 2).
- a multilayer sheet having a three-layer structure composed of three kinds of resin compositions containing a homopolypropylene, an ethylene-propylene copolymer, and a nucleating agent has been proposed (see Patent Document 3).
- transparent polypropylene sheets that are generally produced by an additive formulation such as a nucleating agent or a rapid cooling method using a belt process have a large spherulite structure because the microstructure is destroyed in vacuum forming that requires heating to the melting point or higher. Is generated and transparency is lost. Further, when a component having a softening point lower than that of polypropylene is added to prevent loss of transparency, the white turbidity of the polypropylene sheet is reduced, but there is a problem that the sheet surface is roughened due to the influence of the low-temperature softening point component. Furthermore, in a molded body having a relatively large shape, such as a molded body for a vending machine display, and having a complicated shape such as an uneven shape or a plastic bottle shape, excellent vacuum formability is required. It is difficult to achieve both transparency.
- the sheet described in Patent Document 1 is not sufficient in terms of transparency of the molded body because the surface of the sheet is roughened during vacuum forming and the transparency is lowered.
- seat of patent document 2 there exists a problem that vacuum forming property is insufficient because the softening point at the time of vacuum forming is too high with the problem that a sheet
- seat of patent document 2 is not enough at the point of vacuum moldability and the transparency of a molded object.
- the sheet described in Patent Document 3 is not sufficient in terms of vacuum formability and transparency of the molded body.
- the sheet described in Patent Document 3 uses an ethylene propylene copolymer, there is a problem that heat resistance and rigidity are insufficient.
- the present invention provides a transparent multilayer sheet that has excellent vacuum formability and that can sufficiently prevent whitening during molding to obtain a molded article having high transparency, and a molded article using the same.
- the purpose is to provide.
- the present invention provides the following transparent multilayer sheet and molded article. That is, the transparent multilayer sheet of the present invention includes a base material layer and a surface layer laminated on at least one side of the base material layer, and the base material layer has a storage elastic modulus at a temperature of 23 ° C. and a frequency of 1 Hz. It is characterized by being made of a resin composition having a storage elastic modulus of 2300 MPa or more, a storage elastic modulus at a temperature of 140 ° C. and a frequency of 1 Hz of 150 MPa or less, and a crystallization rate of 1 min ⁇ 1 or more.
- the said base material layer and the said surface layer consist of a resin composition containing a polypropylene-type polymer.
- the base material layer comprises a petroleum polymer having a softening point of from 79.5% by mass to 89.8% by mass and from 110 ° C. to 170 ° C. from 10% by mass to 20% by mass. It is preferably made of a resin composition containing not more than mass% and a nucleating agent of not less than 0.2 mass% and not more than 0.5 mass%.
- the thickness ratio of the surface layer to the substrate layer (the total thickness of the surface layer / the thickness of the substrate layer) is from 1/99 to 20/80, The thickness is preferably 150 ⁇ m or more and 700 ⁇ m or less.
- the transparent multilayer sheet of the present invention preferably has a haze value of 10% or less.
- the molded body of the present invention is characterized by being molded from the transparent multilayer sheet.
- the molded body of the present invention is preferably molded by vacuum molding.
- the molded product of the present invention preferably has a haze value of 15% or less.
- the molded body of the present invention is preferably used for a vending machine display.
- a transparent multilayer sheet having excellent vacuum formability and capable of obtaining a molded article having high transparency by sufficiently preventing whitening during molding, and a molded article using the same Can provide.
- the transparent multilayer sheet of the present invention comprises a base material layer and a surface layer laminated on at least one side of the base material layer, and the base material layer comprises a resin composition that satisfies the conditions described below. It is characterized by.
- the storage elastic modulus (G ′) at a temperature of 23 ° C. and a vibration frequency of 1 Hz is 2300 MPa or more, and the storage elastic modulus (G ′) at a temperature of 140 ° C. and a vibration frequency of 1 Hz is 150 MPa or less. It is necessary to be.
- the storage elastic modulus (G ′) is a parameter as described below. That is, a viscoelastic body such as a resin composition has both viscosity and elasticity. In the case of an ideal elastic body, stress and strain are observed in the same phase. On the other hand, in the case of an ideal liquid, the strain phase is delayed by 90 degrees with respect to the stress phase.
- the viscoelastic body exhibits an intermediate behavior, and the phase difference is between 0 and 90 degrees.
- the elastic modulus can be expressed as a complex elastic modulus G * by a complex number as a ratio of stress ( ⁇ * ) and strain ( ⁇ * ) as in the following formula (F1).
- G * G ' + iG "(F2)
- G ′ in the real part represents the elastic part of the viscoelasticity
- G ′′ represents the viscous part because it is in a phase delayed by 90 degrees.
- G ′ represents the storage elastic modulus and G ′′ represents the loss elastic modulus.
- the storage elastic modulus (G ′) by setting the storage elastic modulus (G ′) within the above range, it has excellent rigidity at room temperature, and has good moldability while maintaining transparency during molding such as vacuum molding. A transparent multilayer sheet can be obtained.
- the storage elastic modulus (G ′) at a temperature of 23 ° C. and a vibration frequency of 1 Hz is 2300 MPa or more, the rigidity at room temperature is excellent. High strength of the fitting part to the instrument can be achieved together.
- the storage elastic modulus (G ′) is more preferably 2400 MPa or more, and particularly preferably 2600 MPa or more from the above viewpoint.
- the storage elastic modulus (G ′) can be measured by the method described in Examples described later.
- this storage elastic modulus (G ′) is more preferably 100 MPa or less, and particularly preferably 90 MPa or less, from the above viewpoint.
- the crystallization rate needs to be 1 min ⁇ 1 or more.
- the cooling time during vacuum forming can be shortened, and whitening due to crystal growth caused by the heat of the mold can be prevented. Thereby, high transparency can be achieved.
- the crystallization rate is more preferably 2.3 min ⁇ 1 or more from the above viewpoint.
- the crystallization rate can be measured by the method described in Examples described later.
- the resin composition used for the base material layer preferably has a haze value that satisfies the following conditions when a transparent multilayer sheet is produced. That is, the haze value of such a transparent multilayer sheet is preferably 10% or less, and more preferably 8.5% or less. In addition, a haze value can be measured by the method as described in the Example mentioned later.
- the resin composition used for the base material layer is not particularly limited as long as the resin composition satisfies the above conditions, and examples thereof include a resin composition containing a polypropylene polymer, a petroleum resin, and a nucleating agent. .
- polypropylene polymer examples include homopolypropylene, polypropylene random copolymer, and polypropylene block copolymer.
- homopolypropylene is preferable from the viewpoint of excellent heat resistance and rigidity.
- these can be used individually by 1 type or in combination of 2 or more types.
- the polypropylene polymer preferably has a stereoregularity (isotactic pentad fraction) of 0.92 or more. If the stereoregularity is less than the lower limit, the heat resistance and rigidity tend to decrease.
- the isotactic pentad fraction is A.I. It can be measured by a method based on the description of 13 C-NMR method (Macromolecules, vol 6, 925, 1973) disclosed by Zambelli.
- the melt flow rate is preferably 0.5 g / 10 min or more and 5 g / 10 min or less. If the melt flow rate is less than the lower limit, the melt viscosity of the resin composition tends to be high, and the elongation at the time of molding tends to be poor.On the other hand, if the upper limit is exceeded, the drawdown at the time of molding is increased, and the moldability is increased. It tends to get worse.
- the content of the polypropylene polymer is preferably 79.5% by mass or more and 89.8% by mass or less based on the resin composition used for the base material layer.
- the petroleum resin preferably has a softening point of 110 ° C. or higher and 170 ° C. or lower.
- the softening point is less than the lower limit, the heat resistance is lowered and the resin component tends to bleed out to the surface in a high temperature atmosphere.
- the upper limit is exceeded, the melting point of the polypropylene polymer is exceeded.
- the sheet softening effect tends not to be imparted in a molding temperature region where the molded body does not whiten.
- Examples of such petroleum resins include aromatic, aliphatic, aromatic hydrocarbon resin-based, alicyclic saturated hydrocarbon resin-based, copolymer-based petroleum resins, and the like.
- a copolymer petroleum resin containing an aromatic component is preferable.
- a copolymer petroleum resin of an aromatic component and dicyclopentadiene is more preferable.
- these can be used individually by 1 type or in combination of 2 or more types.
- the said petroleum resin can be used individually by 1 type or in combination of 2 or more types, it is more preferable to use combining 2 or more types of petroleum resins from which a softening point differs. In such a case, a petroleum resin having a softening point of 140 ° C. or higher and 150 ° C. or lower and a petroleum resin whose softening point is 20 ° C. to 30 ° C.
- the number average molecular weight of the petroleum resin is preferably 720 or more and 1085 or less.
- the number average molecular weight is less than the lower limit, the heat resistance is lowered and the resin component tends to bleed out to the surface in a high temperature atmosphere.
- the upper limit is exceeded, the melting point of the polypropylene polymer is exceeded. Therefore, it tends to be difficult to give the effect of softening the sheet in a molding temperature region where the molded body does not whiten.
- the content of the petroleum resin is preferably 10% by mass or more and 20% by mass or less, and more preferably 13% by mass or more and 16% by mass or less with respect to the resin composition used for the base material layer.
- the content exceeds the upper limit, the heat resistance of the molded body is lowered, and the shape tends to be difficult to maintain in a high-temperature atmosphere.
- the lower limit or lower the molded body is not whitened. The softening of the sheet becomes insufficient, and the vacuum formability tends to decrease.
- the storage elastic modulus (G ′) at a temperature of 23 ° C.
- a vibration frequency of 1 Hz is 2300 MPa or more
- the storage elastic modulus (G ′) at a temperature of 140 ° C. and a vibration frequency of 1 Hz is 150 MPa or less.
- nucleating agent examples include carboxylic acid metal salts, phosphate metal salts, rosin metal salts, talc, mica, and sorbitol derivatives. Among these, it is preferable to use a sorbitol derivative from the viewpoint of improving the transparency of the molded body.
- the content of the nucleating agent is preferably 0.2% by mass or more and 0.5% by mass or less, and preferably 0.25% by mass or more and 0.4% by mass with respect to the resin composition used for the substrate layer. % Or less, more preferably 0.3% by mass or more and 0.35% by mass or less. If the content is less than the lower limit, the crystallization rate of the resin composition tends to decrease and the transparency of the molded product tends to decrease. On the other hand, if the content exceeds the upper limit, the nucleating agent bleeds out and becomes sticky. , Tend to cause poor appearance.
- the nucleating agent is added It is preferable to use within the range.
- additives may be further added to the resin composition used for the base material layer as necessary.
- an elastomer may be added to the resin composition used for the base material layer from the viewpoint of reducing cracks and burrs during cutting and punching of the molded body.
- the resin composition used for the substrate layer may further contain pigments, antistatic agents, antifogging agents, stabilizers, lubricants and the like.
- the resin composition used for the said surface layer is not specifically limited,
- the resin composition containing a polypropylene-type polymer and a nucleating agent is mentioned.
- the polypropylene-based polymer and the nucleating agent those similar to the polypropylene-based polymer and the nucleating agent used in the resin composition used for the base material layer can be used.
- content of the said polypropylene-type polymer is 99.5 mass% or more and 99.8 mass% or less with respect to the resin composition used for the said surface layer. It is preferable that content of the said nucleating agent is 0.2 mass% or more and 0.5 mass% or less with respect to the resin composition used for the said base material layer. If the content is less than the lower limit, the crystallization rate of the resin composition tends to decrease, and the transparency of the surface of the molded product tends to decrease. On the other hand, if the upper limit is exceeded, the nucleating agent bleeds out. It tends to cause stickiness and poor appearance.
- additives may be further added to the resin composition used for the surface layer as necessary.
- pigments, antistatic agents, antifogging agents, stabilizers, lubricants and the like may be further added to the resin composition used for the base material layer.
- the transparent multilayer sheet of this invention is equipped with the said base material layer and the said surface layer laminated
- the thickness ratio of the surface layer to the substrate layer is preferably 1/99 or more and 20/80 or less. More preferably, it is 95 or more and 15/85 or less. If the thickness ratio is less than the lower limit, the surface heat resistance is reduced and surface roughness during molding tends to occur, and the transparency of the molded product tends to decrease. The softening temperature of the resin becomes high, and it tends to be difficult to mold in a temperature range in which the transparency of the molded product can be maintained.
- the thickness of the transparent multilayer sheet is not particularly limited, but is preferably 150 ⁇ m or more and 700 ⁇ m or less, and more preferably 400 ⁇ m or more and 600 ⁇ m or less. If the thickness is less than the lower limit, it tends to be difficult to ensure the strength of the molded body, and if it exceeds the upper limit, it tends to be difficult to form by vacuum forming or the like.
- the transparent multilayer sheet may include an ink easy adhesion layer formed on at least a part of the surface layer.
- an ink easy-adhesion layer By such an ink easy-adhesion layer, the surface layer can be provided with adhesion to ink.
- the surface tension of such an ink easy-adhesion layer is preferably 45 mN / m or more from the viewpoint of adhesion to ink.
- the transparent multilayer sheet has excellent vacuum formability. Therefore, the transparent multilayer sheet is preferably formed by vacuum forming.
- the method for forming the transparent multilayer sheet is not particularly limited.
- the manufacturing apparatus shown in FIG. 1 includes a T die 12, a first cooling roll 13, a second cooling roll 14, a metal endless belt 15, a third cooling roll 16, and a fourth cooling roll 17 connected to a plurality of extruders. Is provided.
- the transparent multilayer sheet and the molded product of the present invention can be produced as follows.
- the first cooling roll 13 is maintained so that the surface temperatures of the endless belt 15 and the third cooling roll 16 that are in direct contact with the transparent multilayer sheet 11 are maintained at a predetermined cooling temperature (for example, 20 ° C. or more and 140 ° C. or less).
- a predetermined cooling temperature for example, 20 ° C. or more and 140 ° C. or less.
- the temperature of the second cooling roll 14 and the third cooling roll 16 is controlled.
- the transparent multilayer sheet 11 extruded from the T-die 12 is brought into contact with the endless belt 15 that is in contact with the first cooling roll 13 and the third cooling roll 16 almost simultaneously, so that the first cooling roll 13 and the first cooling roll 13 Introduced between the three cooling rolls 16.
- the first cooling roll 13 has a surface coated with an elastic material 18.
- the endless belt 15 and the third cooling roll 16 preferably have a mirror surface with a surface roughness of, for example, 0.5 S or less.
- the transparent multilayer sheet 11 is press-contacted with the 1st cooling roll 13 and the 3rd cooling roll 16, and it cools below to crystallization temperature.
- the transparent multilayer sheet 11 can be unwound from the 2nd cooling roll 14 and the 4th cooling roll 17, and the transparent multilayer sheet 11 of this invention can be obtained.
- an ink easy-adhesion layer is formed on part of the surface layer of the transparent multilayer sheet 11 of the present invention, for example, a method such as a gravure coating method can be employed.
- the molded article of the present invention is characterized by being molded from the transparent multilayer sheet of the present invention. Since such a molded body is formed from the above-described transparent multilayer sheet of the present invention, it has high transparency by sufficiently preventing whitening during molding. And it is preferable that the haze value of such a molded object is 15% or less (more preferably 13% or less). Moreover, since the above-mentioned transparent multilayer sheet of the present invention has excellent vacuum formability, such a formed body can be formed into a highly designable body. Specifically, the molded article of the present invention can be suitably used as a molded article for a vending machine display.
- the method for forming the molded body of the present invention from the transparent multilayer sheet of the present invention is not particularly limited, and for example, a molding method such as vacuum molding, pressure molding, vacuum pressure molding, press molding, or the like can be employed.
- Crystallization speed was measured using a differential scanning calorimeter (DSC) (manufactured by Perkin Elmer, product name “Diamond DSC”). Specifically, first, a sample having a weight of 5 g is prepared using the resin composition. The sample was heated from 50 ° C. to 230 ° C. at 80 ° C./min, held at 230 ° C. for 5 minutes, cooled from 230 ° C. to 130 ° C.
- DSC differential scanning calorimeter
- the total light transmittance of the sample was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name “NDH200”).
- Vacuum formability The vacuum formability of the sheet was evaluated by visually confirming the mold reproducibility of the edge of the outer peripheral portion of the obtained molded body. When the edge mold reproducibility was excellent, it was determined as “good”, and in other cases, it was determined as “bad”.
- Appearance The appearance of the obtained molded body was visually evaluated. When there was no surface roughness and whitening, it was determined as “good”, and when there was whitening, it was determined as “whitening”.
- Example 1 to Example 5 and Comparative Example 1 to Comparative Example 3 First, resin compositions were prepared according to the compositions shown in Tables 1 and 2 using the following polypropylene-based polymer, petroleum resin, nucleating agent, and additives to obtain pellets of the resin composition. Regarding the resin composition for the base material layer among the obtained resin compositions, the properties (storage elastic modulus, crystallization speed) of the resin composition were evaluated, and the obtained results are shown in Table 1 and Table 2. .
- Polypropylene polymer Homopolypropylene (manufactured by Sun Allomer Co., Ltd., trade name “PL500A”)
- Petroleum resin-1 Petroleum resin (softening point: 140 ° C., number average molecular weight: 900, manufactured by Idemitsu Kosan Co., Ltd., trade name “P-140”)
- Petroleum resin-2 Petroleum resin (softening point: 125 ° C., number average molecular weight: 820, manufactured by Idemitsu Kosan Co., Ltd., trade name “P-125”)
- Nucleator Sorbitol derivative (Sorbitol derivative masterbatch, manufactured by Riken Vitamin Co., Ltd., trade name “Rike Master PN-10R”)
- Elastomer Polystyrene-poly (ethylene / propylene) block-polystyrene copolymer (Kuraray Co., Ltd., trade name “Septon 2004”)
- Blue pigment Blue pigment (manufactured by Dain
- pellets of the resin composition are prepared according to the composition (unit: mass%) shown in Table 1 and Table 2, and charged into an extruder. However, about the blue pigment among the said composition, it is the addition amount when the total amount of a resin composition is 100 mass parts.
- the resin temperature is melt extruded at 240 ° C. to obtain a sheet-shaped resin composition, and this sheet-shaped resin composition is mixed with the endless belt 15 on the first cooling roll 13, The sheet was quenched between the three cooling rolls 16 while being pressed in a planar manner, and the transparent multilayer sheet 11 having a sheet thickness of 500 mm was obtained at a speed of 2.5 m / min.
- the obtained transparent multilayer sheet 11 has a three-layer structure of surface layer / base material layer / surface layer.
- Tables 1 and 2 show the thickness and thickness ratio (total thickness of the surface layer / thickness of the base material layer) of the obtained transparent multilayer sheet 11.
- the obtained transparent multilayer sheet 11 was molded by a vacuum molding machine (Minos Co., Ltd., product name “FH-3M / H type single plate molding machine”) for evaluation of the display can shape. A molded body was obtained. The properties of the obtained multilayer sheet and the obtained molded product were evaluated, and the obtained results are shown in Tables 1 and 2.
- the resin composition used for the base material layer has a storage elastic modulus of 2300 MPa or more at a temperature of 23 ° C. and a frequency of 1 Hz, and a temperature of 140 ° C. and a frequency of 1 Hz.
- the storage elastic modulus is 150 MPa or less and the crystallization rate is 1 min ⁇ 1 or more are satisfied (Examples 1 to 5)
- the film has excellent vacuum formability and at the time of molding. It was confirmed that a molded body having high transparency can be obtained by sufficiently preventing whitening of the resin.
- the transparent multilayer sheet of the present invention is suitably used as a transparent multilayer sheet used in applications such as vending machine displays and industrial material decoration.
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Abstract
Description
すなわち、本発明の透明多層シートは、基材層と、前記基材層の少なくとも片面に積層された表面層とを備え、前記基材層は、温度23℃、振動数1Hzにおける貯蔵弾性率が2300MPa以上であり、温度140℃、振動数1Hzにおける貯蔵弾性率が150MPa以下であり、かつ結晶化速度が1min-1以上である樹脂組成物からなることを特徴とするものである。
本発明の透明多層シートにおいては、前記基材層が、ポリプロピレン系重合体79.5質量%以上89.8質量%以下、110℃以上170℃以下の軟化点を有する石油樹脂10質量%以上20質量%以下、および、造核剤0.2質量%以上0.5質量%以下を含む樹脂組成物からなることが好ましい。
本発明の透明多層シートにおいては、前記基材層に対する前記表面層の厚み比(表面層の総厚み/基材層の厚み)が1/99以上20/80以下であり、該透明多層シートの厚みが150μm以上700μm以下であることが好ましい。
本発明の透明多層シートは、ヘイズ値が10%以下であるものであることが好ましい。
本発明の成形体は、真空成形により成形されたものであることが好ましい。
本発明の成形体は、ヘイズ値が15%以下であることが好ましい。
本発明の成形体においては、自動販売機ディスプレイに用いるものであることが好ましい。
先ず、本発明の透明多層シートについて説明する。すなわち、本発明の透明多層シートは、基材層と、前記基材層の少なくとも片面に積層された表面層とを備え、前記基材層は、以下説明する条件を満たす樹脂組成物からなることを特徴とするものである。
ここで、貯蔵弾性率(G’)は、以下に説明するようなパラメータである。すなわち、樹脂組成物のような粘弾性体は、粘性と弾性を兼ね備えて持っている。理想弾性体の場合は、応力とひずみは同一位相で観察される。一方で理想液体の場合は、応力の位相に対してひずみの位相は90度遅れる。粘弾性体はその中間の挙動を示し、位相差は0度から90度の間の値となる。
弾性率は応力(σ*)とひずみ(γ*)の比として複素数により複素弾性率G*として、下記数式(F1)のように表現できる。
G*=σ*/γ*=(σ0/γ0)eiδ=(σ0/γ0)(cosδ+isinδ) ・・・(F1)
複素弾性率G*を実数部分と虚数部分に分けて、下記数式(F2):
G*=G’+iG” ・・・(F2)
としたとき、実数部分のG’は粘弾性のうち弾性部分、G”はそれより90度遅れた位相にあるので粘性部分を表す。G’は貯蔵弾性率、G”は損失弾性率を呼ばれ、測定試料に振動変形を加え、ひずみの振幅と力計で検出される応力の振幅およびそれらの間の位相差を測定すると、粘弾性体の弾性の寄与、粘性の寄与が評価できる。
本発明においては、貯蔵弾性率(G’)を前記範囲内とすることで、室温において優れた剛性を有し、例えば真空成形のような成形時には透明性を維持しながら良好な成形性を有する透明多層シートを得ることができる。
前記ポリプロピレン系重合体においては、立体規則性(アイソタクティックペンタッド分率)が0.92以上であることが好ましい。立体規則性が前記下限未満では、耐熱性および剛性が低下する傾向にある。なお、アイソタクティックペンタッド分率は、A.Zambelliにより開示された13C-NMR法(Macromolecules,vol6,925,1973)の記載に準拠する方法で測定できる。
前記ポリプロピレン系重合体の含有量は、前記基材層に用いる樹脂組成物に対して、79.5質量%以上89.8質量%以下であることが好ましい。
このような石油樹脂としては、例えば、芳香族系、脂肪族系、芳香族炭化水素樹脂系、脂環族飽和炭化水素樹脂系、共重合系等の石油樹脂が挙げられる。これらの中でも、透明性と成形性という観点から、芳香族成分を含む共重合系石油樹脂が好ましい。また、これらの中でも、前記の観点から、芳香族成分とジシクロペンタジエンとの共重合系石油樹脂が更に好ましい。また、これらは1種を単独でまたは2種以上を組み合わせて使用することができる。
前記石油樹脂は1種を単独でまたは2種以上を組み合わせて使用することができるが、軟化点の異なる2種以上の石油樹脂を組み合わせて使用することがより好ましい。このような場合において、軟化点が140℃以上150℃以下の石油樹脂に対して、この石油樹脂と比べて軟化点が20℃から30℃低い石油樹脂を、これらの質量比(低軟化点石油樹脂/高軟化点石油樹脂)が1/10以上1/1以下となるように、添加することがより好ましい。このようにすることで、真空成形時に良好な型再現性を得られる温度範囲が広くなり、加工性を更に向上できる。
前記基材層に用いる樹脂組成物において、温度23℃、振動数1Hzにおける貯蔵弾性率(G’)が2300MPa以上であり、温度140℃、振動数1Hzにおける貯蔵弾性率(G’)が150MPa以下であるという条件を達成するためには、前記石油樹脂を前記範囲内で使用することが好ましい。
前記基材層に用いる樹脂組成物において、結晶化速度が1min-1以上という条件を達成し、得られる透明多層シートでのべた付きや外観不良を抑制するためには、前記造核剤を前記範囲内で使用することが好ましい。
ポリプロピレン系重合体および造核剤としては、前記基材層に用いる樹脂組成物で用いるポリプロピレン系重合体および造核剤と同様のものを用いることができる。
前記造核剤の含有量は、前記基材層に用いる樹脂組成物に対して、0.2質量%以上0.5質量%以下であることが好ましい。含有量が前記下限未満では、樹脂組成物の結晶化速度が低下して、成形体の表面の透明性が低下する傾向にあり、他方、前記上限を超えると、造核剤がブリードアウトしてべた付き、外観不良の原因となる傾向にある。
このような透明多層シートにおいては、前記基材層に対する前記表面層の厚み比(表面層の総厚み/基材層の厚み)が1/99以上20/80以下であることが好ましく、5/95以上15/85以下であることがより好ましい。厚み比が前記下限未満では、表面の耐熱性が低下するために成形時の表面荒れが発生して、成形体の透明性が低下する傾向にあり、他方、前記上限を超えると、シート全体での軟化温度が高くなり、成形品の透明性を維持できる温度範囲で成形しにくくなる傾向にある。
このようなインク易接着層の表面張力は、インクとの接着性の観点から、45mN/m以上であることが好ましい。
第一冷却ロール13は、その表面に弾性材18が被覆されている。エンドレスベルト15および第三冷却ロール16は、好ましくは表面粗さが、例えば0.5S以下の鏡面を有している。
そして、第一冷却ロール13および第三冷却ロール16で透明多層シート11を圧接して結晶化温度以下に冷却する。このようにして、透明多層シート11の圧接と冷却とを同時に行うことが可能になり、透明多層シート11の透明性を高めることができる。この際、第一冷却ロール13と第三冷却ロール16間の押圧力で弾性材18が圧縮されて弾性変形し、透明多層シート11は、両冷却ロール13,16による面状圧接となっている。
その後、透明多層シート11を、第二冷却ロール14および第四冷却ロール17から巻き出して、本発明の透明多層シート11を得ることができる。
このような成形体は、前述した本発明の透明多層シートから成形されたものであるため、成形時の白化を十分に防止して高い透明性を有している。そして、このような成形体のヘイズ値は15%以下(より好ましくは13%以下)であることが好ましい。
また、このような成形体は、前述した本発明の透明多層シートが優れた真空成形性を有しているため、意匠性の高い成形体とすることができる。具体的には、本発明の成形体は、自動販売機ディスプレイ用の成形体として好適に用いることができる。
(1)貯蔵弾性率
粘弾性スペクトロメーター(セイコーインスツル株式会社製、製品名「EXSTAR DMS6100」)を用いて、貯蔵弾性率を測定した。具体的には、先ず、樹脂組成物を用いて幅4.0mm、厚み0.5mmの試料を作製する。そして、スパン間距離20mmとなるよう設定し、昇温速度2℃/min、周波数1Hzの条件で0℃から融点まで測定を行い、得られたデータから23℃と140℃における貯蔵弾性率を得た。
(2)結晶化速度
示差走査熱量測定器(DSC)(パーキンエルマー社製、製品名「Diamond DSC」)を用いて、結晶化速度を測定した。具体的には、先ず、樹脂組成物を用いて重量5gの試料を作製する。そして、試料を80℃/minにて50℃から230℃に昇温し、230℃にて5分間保持し、80℃/minで230℃から130℃に冷却し、その後130℃に保持して結晶化を行う。130℃になった時点から熱量変化について測定を開始して、DSC曲線を得た。
得られたDSC曲線から、以下の手順(i)~(iv)により結晶化速度を求めた。
(i)測定開始からピークトップまでの時間の10倍の時点から、20倍の時点までの熱量変化を直線で近似したものをベースラインとした。
(ii)ピークの変曲点における接線とベースラインとの交点を求め、結晶化開始および終了温度を求めた。
(iii)得られた結晶化開始温度から、ピークトップまでの時間を結晶化時間として測定した。
(iv)得られた結晶化時間の逆数から、結晶化速度を求めた。
(3)ヘイズ値
JIS K7136に記載の方法に準拠して、ヘイズ値を測定した。具体的には、ヘイズメータ(日本電色工業株式会社製、製品名「NDH200」)を用いて、試料のヘイズ値を測定した。
(4)全光線透過率
JIS K7105に記載の方法に準拠して、全光線透過率を測定した。具体的には、ヘイズメータ(日本電色工業株式会社製、製品名「NDH200」)を用いて、試料の全光線透過率を測定した。
(5)真空成形性
得られた成形体における外周部分のエッジの型再現性を目視にて確認することで、シートの真空成形性を評価した。エッジの型再現性に優れる場合には「良好」と判定し、それ以外の場合には「不良」と判定した。
(6)外観
得られた成形体の外観を目視にて評価した。表面荒れおよび白化がない場合には「良好」と判定し、白化がある場合には「白化」と判定した。
先ず、以下に示すポリプロピレン系重合体、石油樹脂、造核剤および添加剤を用いて、表1および表2に示す組成にしたがって樹脂組成物を調製し、樹脂組成物のペレットとした。得られた樹脂組成物のうちの基材層用の樹脂組成物については、樹脂組成物の特性(貯蔵弾性率、結晶化速度)を評価し、得られた結果を表1および表2に示す。
ポリプロピレン系重合体:ホモポリプロピレン(サンアロマー株式会社製、商品名「PL500A」)
石油樹脂-1:石油樹脂(軟化点:140℃、数平均分子量:900、出光興産株式会社製、商品名「P-140」)
石油樹脂-2:石油樹脂(軟化点:125℃、数平均分子量:820、出光興産株式会社製、商品名「P-125」)
造核剤:ソルビトール誘導体(理研ビタミン株式会社製ソルビトール誘導体マスターバッチ、商品名「リケマスターPN-10R」)
エラストマー:ポリスチレン-ポリ(エチレン/プロピレン)ブロック-ポリスチレン共重合体(株式会社クラレ製、商品名「セプトン2004」)
青色顔料:青色顔料(大日精化工業株式会社製、商品名「PP-RM 10G787」)
次いで、得られた透明多層シート11を用いて、真空成型機(株式会社ミノス社製、製品名「FH-3M/H型 単板成形機」)により成形して、ディスプレイ缶形状の評価用の成形体を得た。得られた多層シートおよび得られた成形体の特性を評価し、得られた結果を表1および表2に示す。
表1および表2に示した結果から明らかなように、基材層に用いる樹脂組成物が、温度23℃、振動数1Hzにおける貯蔵弾性率が2300MPa以上であり、温度140℃、振動数1Hzにおける貯蔵弾性率が150MPa以下であり、かつ結晶化速度が1min-1以上であるという条件を全て満たす場合(実施例1から実施例5)には、優れた真空成形性を有し、かつ成形時の白化を十分に防止して高い透明性を有する成形体を得ることができることが確認された。
Claims (9)
- 基材層と、前記基材層の少なくとも片面に積層された表面層とを備え、
前記基材層は、温度23℃、振動数1Hzにおける貯蔵弾性率が2300MPa以上であり、温度140℃、振動数1Hzにおける貯蔵弾性率が150MPa以下であり、かつ結晶化速度が1min-1以上である樹脂組成物からなる
ことを特徴とする透明多層シート。 - 請求項1に記載の透明多層シートにおいて、
前記基材層および前記表面層がポリプロピレン系重合体を含む樹脂組成物からなる
ことを特徴とする透明多層シート。 - 請求項1または請求項2に記載の透明多層シートにおいて、
前記基材層が、ポリプロピレン系重合体79.5質量%以上89.8質量%以下、110℃以上170℃以下の軟化点を有する石油樹脂10質量%以上20質量%以下、および、造核剤0.2質量%以上0.5質量%以下を含む樹脂組成物からなる
ことを特徴とする透明多層シート。 - 請求項1から請求項3までのいずれか1項に記載の透明多層シートにおいて、
前記基材層に対する前記表面層の厚み比(表面層の総厚み/基材層の厚み)が1/99以上20/80以下であり、
該透明多層シートの厚みが150μm以上700μm以下である
ことを特徴とする透明多層シート。 - 請求項1から請求項4までのいずれか1項に記載の透明多層シートにおいて、
ヘイズ値が10%以下であるものである
ことを特徴とする透明多層シート。 - 請求項1から請求項5までのいずれか1項に記載の透明多層シートから成形されたことを特徴とする成形体。
- 請求項6に記載の成形体であって、
真空成形により成形されたものである
ことを特徴とする成形体。 - 請求項6または請求項7に記載の成形体であって、
ヘイズ値が15%以下である
ことを特徴とする成形体。 - 請求項6から請求項8までのいずれか1項に記載の成形体であって、
自動販売機ディスプレイに用いるものである
ことを特徴とする成形体。
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- 2011-12-26 CN CN201180063639.9A patent/CN103442889B/zh not_active Expired - Fee Related
- 2011-12-26 EP EP20110853178 patent/EP2660046A4/en not_active Withdrawn
- 2011-12-26 US US13/977,269 patent/US20130280507A1/en not_active Abandoned
- 2011-12-26 KR KR1020137016328A patent/KR20130141613A/ko not_active Application Discontinuation
- 2011-12-26 WO PCT/JP2011/080008 patent/WO2012090902A1/ja active Application Filing
- 2011-12-28 TW TW100149328A patent/TW201231523A/zh unknown
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JPH07186346A (ja) * | 1993-12-27 | 1995-07-25 | Sumitomo Bakelite Co Ltd | Ptp用多層ポリプロピレンシート |
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JPH11129417A (ja) * | 1997-10-31 | 1999-05-18 | Sumitomo Bakelite Co Ltd | Pp系ptp用シート |
JP2002284942A (ja) * | 2001-03-27 | 2002-10-03 | Grand Polymer Co Ltd | 結晶性ポリプロピレン樹脂組成物およびそれから製造されるシート |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014157320A1 (ja) * | 2013-03-29 | 2014-10-02 | 出光ユニテック株式会社 | 積層体、成形体、成形物、および、成形物の製造方法 |
JP2014198416A (ja) * | 2013-03-29 | 2014-10-23 | 出光ユニテック株式会社 | 成形物およびその製造方法 |
JP2014198414A (ja) * | 2013-03-29 | 2014-10-23 | 出光ユニテック株式会社 | 積層体、成形体、成形物、および、成形物の製造方法 |
EP2979865A4 (en) * | 2013-03-29 | 2017-03-22 | Idemitsu Unitech Co. Ltd. | Laminated body, molded body, molded product, and method for manufacturing molded product |
US10239290B2 (en) | 2013-03-29 | 2019-03-26 | Idemitsu Unitech Co., Ltd. | Laminated body, molded body, molded product, and method for manufacturing molded product |
US10821711B2 (en) | 2013-03-29 | 2020-11-03 | Idemitsu Unitech Co., Ltd. | Laminated body, molded body, molded product, and method for manufacturing molded product |
JP2016068337A (ja) * | 2014-09-29 | 2016-05-09 | 出光ユニテック株式会社 | 積層体、成形体、成形物、および、成形物の製造方法 |
WO2021066132A1 (ja) * | 2019-10-03 | 2021-04-08 | 出光ユニテック株式会社 | 成形体及び成形体の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201231523A (en) | 2012-08-01 |
EP2660046A1 (en) | 2013-11-06 |
CN103442889B (zh) | 2017-02-08 |
KR20130141613A (ko) | 2013-12-26 |
US20130280507A1 (en) | 2013-10-24 |
CN103442889A (zh) | 2013-12-11 |
JP2012139826A (ja) | 2012-07-26 |
JP5763337B2 (ja) | 2015-08-12 |
EP2660046A4 (en) | 2014-06-25 |
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