JP7451954B2 - Laminate and press molding method - Google Patents

Description

The present invention relates to various mold release materials and cushioning materials for use in press molding in printed wiring boards, ICs, semiconductors, passive components, and other display/touch panel related product components and LED lighting product components that are incorporated into electrical and electronic products. (hereinafter referred to as "mold release material etc.").

Silicone resins, represented by silicone rubber, have excellent heat resistance and electrical properties, and are therefore used for applications such as mold release materials.

However, if you try to use a sheet made of silicone rubber as it is as a mold release material for press molding, because it is a rubber product, it will deform, the assembly dimensional accuracy will deteriorate, wrinkles will occur, and the work will be difficult. There was a problem with sexuality.

Therefore, as a silicone rubber composite that can solve the above problems, Patent Document 1 discloses that at least one side of a sheet or film mainly made of crystalline polyester resin has an undercoat layer and a high affinity for the undercoat layer, and A silicone rubber composite has been proposed in which thin film layers containing silicone resin are sequentially formed, a silicone rubber layer made of a silicone elastomer resin having a specific hardness is formed, and the sheet or film and the silicone rubber layer are integrated. There is. These composites are usually stored in stacks, and when used for press molding or the like, they are taken out one by one from the top and placed in a mold for press molding.

Japanese Patent Application Publication No. 11-20082

However, when laminating a resin with a low elastic modulus, that is, a resin with rubber elasticity and a resin with a high elastic modulus, as in the silicone composite of Patent Document 1, the following problems may occur depending on the conditions, and the workability may be reduced. The inventors' studies have revealed that this is insufficient.
- When using stacked silicone composites, if you try to take them out from the top, the lower stacked composites will stick together and you will have to take out multiple pieces at once.
・Due to electrostatic attraction, the laminates adhere to each other and are difficult to peel off, making them difficult to handle.
・When opening the mold or press plate to take out the product after press molding, the silicone composite remains attached to the mold or press plate.
In addition, studies conducted by the present inventors have revealed that the above-mentioned problem becomes more pronounced as the difference in dielectric constant between a resin with a high modulus of elasticity and a resin with a low modulus of elasticity increases.

The present inventors have made extensive studies to solve the above-mentioned problems, and found that in a resin laminate including layers with different elastic moduli, by setting the surface roughness of the layer with a higher elastic modulus within a specific range, It was discovered that the problem of multiple sheets being taken out during use and the problem of adhesion to molds and press plates could be improved, and the present invention was completed.

That is, the gist of the present invention is the following [1] to [14].

[1] A layer (A) whose main component is a resin (a) whose storage modulus at 23°C is 1000 MPa or more, and a layer (b) whose main component is a resin (b) whose storage modulus at 23°C is 100 MPa or less ( B), characterized in that the surface roughness of at least one side of the layer (A) satisfies either or both of the following requirements (i) and (ii): laminate.
(i) 10-point average roughness (Rz) is 0.3 μm or more (ii) Arithmetic average roughness (Ra) is 0.05 μm or more

[2] The laminate according to [1], wherein the maximum height roughness (Ry) of at least one surface of the layer (A) is 0.3 μm or more.

[3] The laminate according to [1] or [2], wherein the average spacing (Sm) of the irregularities on the surface of at least one side of the layer (A) is 90 μm or less.

[4] The surface roughness of at least one side of the layer (B) satisfies either or both of the following requirements (iii) and (iv), according to any one of [1] to [3]. laminate.
(iii) Ten point average roughness (Rz) is 0.3 μm or more (iv) Arithmetic average roughness (Ra) is 0.05 μm or more

[5] The laminate according to any one of [1] to [4], wherein the maximum height roughness (Ry) of at least one surface of the layer (B) is 0.4 μm or more.

[6] The laminate according to any one of [1] to [5], wherein the average spacing (Sm) of the irregularities on the surface of at least one side of the layer (B) is 70 μm or less.

[7] The coefficient of static friction between the layer (A) side surface of one laminate and the layer (B) side surface of the other laminate is 2.1 or less, [1] to [6] The laminate according to any of the above.

[8] The coefficient of dynamic friction between the layer (A) side surface of one laminate and the layer (B) side surface of the other laminate is 1.8 or less, [1] to [7]. The laminate according to any one of the above.

[9] The laminate according to any one of [1] to [8], wherein the dielectric constant difference between the layer (A) and the layer (B) is 0.15 or more.

[10] The laminate according to any one of [1] to [9], wherein the resin (a) is a polyester resin.

[11] The laminate according to any one of [1] to [10], wherein the resin (b) is a silicone resin.

[12] The laminate according to any one of [1] to [11], wherein the resin (a) is a polyethylene terephthalate resin.

The laminate according to any one of [1] to [12], which is used for press molding.

[14] A press molding method using the laminate according to any one of [1] to [13], wherein the layer (B) is placed between the laminate and the laminate so that the layer (B) side is the molded product side. A press molding method characterized by arranging a molded body.

According to the present invention, it is possible to provide a laminate that is difficult to adhere to each other and has excellent handling properties.

The present invention will be explained in detail below.
In the present invention, the term "main component" refers to the component that is most present in the target layer, preferably 50% by mass or more, more preferably 70% by mass or more in the target layer. The content is more preferably 80% by mass, particularly preferably 90% by mass or more.
In the present invention, when expressed as "X to Y" (X, Y are arbitrary numbers), unless otherwise specified, it means "more than or equal to X and less than or equal to Y", and also means "preferably greater than It shall include the meaning of "small".

In addition, in the present invention, when expressed as "more than or equal to X" (X is any number), unless otherwise specified, it includes the meaning of "preferably greater than X" and "less than or equal to Y" (where Y is any number). ) shall include the meaning of "preferably smaller than Y" unless otherwise specified.

The storage modulus in the present invention is measured using a sheet-shaped test sample in accordance with JIS K7244-4:1999 at a temperature range of -100 to 250°C, a heating rate of 3°C/min, a vibration frequency of 1Hz, and a strain of 0. 1%, distance between chucks 25 mm, and storage elastic modulus at 23° C. when measured under the conditions of the tensile method.

The 10-point average roughness (Rz), arithmetic average roughness (Ra), maximum height roughness (Ry), and average spacing of unevenness (Sm) in the present invention are based on the old JIS B0601:1994, and the contact roughness This refers to the value measured with a meter.

The static friction coefficient and dynamic friction coefficient in the present invention refer to values measured by the method described in the Examples below with reference to JIS K7125:1999.

The surface resistivity in the present invention refers to a value measured in accordance with JIS K6911:2006 (5.13).

The relative dielectric constant in the present invention refers to a value measured at 20° C., relative humidity 65%, applied voltage 1 V, and frequency 1 MHz according to JIS C2138:2007.

The laminate of the present invention has a layer (A) mainly composed of a resin (a) having a storage modulus of 1000 MPa or more at 23°C, and a layer (b) mainly comprising a resin (b) having a storage modulus of 100 MPa or less at 23°C. A laminate comprising a layer (B), in which the surface roughness of at least one side of the layer (A) satisfies either or both of the following requirements (i) and (ii): It is.
(i) 10-point average roughness (Rz) is 0.3 μm or more (ii) Arithmetic average roughness (Ra) is 0.05 μm or more

<Layer (A)>
Layer (A) is a layer mainly composed of resin (a) having a storage modulus of 1000 MPa or more at 23°C. The storage modulus of the resin (a) is preferably 2000 MPa or more, more preferably 3000 MPa or more, from the viewpoint of improving handling properties and dimensional accuracy such as suppressing deformation of the laminate when used as a mold release material during press molding. More preferably, it is 4000 MPa or more. Moreover, it is preferably 10,000 MPa or less, more preferably 8,500 MPa or less, still more preferably 7,000 MPa or less, particularly preferably 6,000 MPa or less.
The resin (a) having a storage modulus of 1000 MPa or more at 23°C is not particularly limited, and examples thereof include olefin resins, styrene resins, polyester resins, polycarbonate resins, polyamide resins, polyetherimide resins, Examples include polyphenylene sulfide resin, polyphenylene ether resin, polyaryletherketone resin, liquid crystal polymer resin, polyimide resin, etc., but from the viewpoint of heat resistance and mechanical strength, polyester resin is preferable, and crystalline polyester resin is preferable. It is more preferable that there be some, and examples thereof include polyethylene terephthalate resin, polyethylene naphthalate resin, and the like. Among these, polyethylene terephthalate resin is particularly preferred from the viewpoint of heat resistance, film stiffness, smoothness, ease of commercial availability, etc., as well as adhesiveness with the silicone resin layer described below, especially the silicone elastomer resin layer. .

Layer (A) may contain additives such as ultraviolet absorbers, light stabilizers, antioxidants, plasticizers, nucleating agents, lubricants, pigments, dyes, etc., and storage elasticity at 23°C, within a range that does not impair the effects of the present invention. It may also contain a resin having a modulus of less than 1000 MPa. Further, from the viewpoint of mechanical strength, it is preferable that the layer (A) is at least uniaxially, particularly biaxially stretched.

In the present invention, the surface roughness of at least one side of the layer (A) satisfies either or both of the following requirements (i) and (ii).
(i) Ten point average roughness (Rz) is 0.3 μm or more (ii) Arithmetic average roughness (Ra) is 0.05 μm or more As will be described later, the layer (A) has an antistatic layer ( When A1) is applied, it refers to the surface roughness of the antistatic layer (A1).

Rz is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, particularly preferably 2.5 μm or more, and most preferably 3 μm or more. . When Rz is 0.3 μm or more, when the laminates of the present invention are stacked together, the convex portions come into point contact, which suppresses adhesion of the laminates to each other, making it easy to obtain a laminate with excellent releasability. . Further, the laminate tends to be easily handled when taking out the laminate one by one. Furthermore, the problem of the laminate adhering to the mold/press plate when the mold/press plate is opened to take out the product after press molding is alleviated, and productivity tends to be improved. Furthermore, it has the advantage of making good contact with the molded product, press plate, and mold, and making positioning on the press-formed product easier.

Moreover, Rz is preferably 10 μm or less, more preferably 8 μm or less, even more preferably 6 μm or less, and particularly preferably 5.5 μm or less. It is preferable that Rz is 10 μm or less, since handling properties when disposed in a molded body, a press plate, or a mold tend to be good, and the dimensional stability of the press-formed body tends to be good.

For the same reason as above, the arithmetic mean roughness (Ra) of the surface of at least one side of the layer (A) is preferably 0.1 μm or more, more preferably 0.3 μm or more, and 0.1 μm or more. It is more preferably .4 μm or more, particularly preferably 0.5 μm or more, and most preferably 0.6 μm or more. Further, Ra is preferably 5 μm or less, more preferably 4 μm or less, even more preferably 3 μm or less, particularly preferably 2 μm or less, and most preferably 1.5 μm or less.

Furthermore, for the same reason as above, the maximum height roughness (Ry) of the surface of at least one side of the layer (A) and the average spacing of the unevenness (Sm) are preferably in the following ranges.
Ry is preferably 0.3 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, particularly preferably 3 μm or more, and most preferably 4 μm or more. Moreover, Ry is preferably 10 μm or less, more preferably 9 μm or less, even more preferably 8 μm or less, particularly preferably 7 μm or less, and most preferably 6.5 μm or less.

Sm is preferably 90 μm or less, more preferably 80 μm or less, even more preferably 70 μm or less, particularly preferably 65 μm or less, and most preferably 60 μm or less. Further, Sm is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more.

Examples of methods for obtaining the layer (A) having the above-mentioned surface roughness include sandblasting, shotblasting, etching, engraving, embossing roll transfer, embossing belt transfer, embossing film transfer, surface crystallization, etc. Various methods can be used. In particular, a method using sandblasting is preferred because it is an environmentally friendly processing method that does not use organic solvents, and it is possible to continuously and uniformly form surface irregularities while feeding the roll film.
In the sandblasting process, a layer (A) having a desired surface roughness can be obtained by adjusting the particle size of the sandblasting particles, the blasting pressure, etc.

The thickness of layer (A) is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more. It is preferable that the thickness of the layer (A) is 10 μm or more because wrinkles and the like are less likely to occur when other layers such as the layer (B) described below are laminated on the surface of the layer (A). On the other hand, the thickness is preferably 350 μm or less, more preferably 300 μm or less, and even more preferably 250 μm or less. It is preferable that the thickness of the layer (A) is 350 μm or less, since the resulting laminate will not be too hard and will be easier to coat with an undercoat layer, etc., which will be described later.

In the present invention, it is also preferable that the surface resistivity of the side of the layer (A) on which the layer (B) is not laminated is adjusted to be low, and specifically, the surface resistivity is adjusted to be lower than 1×10 ¹³ Ω. It is preferable that there be. By setting the surface resistivity to less than 1×10 ¹³ Ω, adhesion when stacking the laminates of the present invention is suppressed, and a laminate with excellent releasability tends to be obtained. In addition, the laminate tends to have excellent handling properties when taking out the laminate one by one. Furthermore, when the mold/press plate is opened after press molding and the product is taken out, the problem of the laminate adhering to the mold/press plate side is less likely to occur, and productivity tends to improve. Furthermore, there is also the advantage that the contact condition with the molded object, press plate, and mold becomes good, making positioning easier.

The surface resistivity is more preferably 1×10 ¹² Ω or less, still more preferably 1×10 ¹¹ Ω or less, particularly preferably 5×10 ¹⁰ Ω or less, especially preferably 1×10 ⁹ Ω or less, most preferably 1×10 ⁸ Ω or less. In addition, the surface resistivity is preferably 1×10 ² Ω or more, more preferably 1×10 ⁴ Ω or more, and 1× More preferably, it is 10 ⁶ Ω or more.

As a method for obtaining the layer (A) having the above-mentioned surface resistivity, it is preferable to employ, for example, the following methods (1) to (4).

(1) An antistatic layer (A1) is formed on the layer (A).
(2) Adding an antistatic agent such as a surfactant to the layer (A).
(3) A conductive filler such as graphite, carbon black, carbon fiber, metal oxide, metal powder, metal fiber, etc. is blended into the layer (A).
(4) Adding a conductive polymer to layer (A).

Among the methods (1) to (4) above, the following points are important: that the surface resistivity can be stably obtained, that it is easy to achieve a lower surface resistivity, that the surface resistivity is less likely to change over time, and that the use of antistatic agents It is preferable to employ method (1) since the problem of bleed-out is less likely to occur. (1) will be explained below.

<Antistatic layer (A1)>
Conventionally known coating methods can be used to form the antistatic layer (A1) on the layer (A), but it is preferable to form the antistatic layer (A1) on the layer (A) after forming the layer (A) in the form of a film or sheet. Examples include so-called off-line coating in which a coating layer is provided, and so-called in-line coating in which a coating layer is provided during the formation of layer (A) into a film or sheet. Preferably, it is provided by in-line coating, particularly by a coating/stretching method in which stretching is performed after coating.

In-line coating is a method in which coating is performed within the film manufacturing process, and specifically, coating is performed at any stage from melt extrusion of the resin to stretching, heat setting, and winding. Usually, it is either a substantially amorphous unstretched sheet obtained by melting and quenching, a stretched uniaxially oriented film, a biaxially oriented film before heat setting, or a film after heat setting before winding. Coat.

Although not limited to the following, for example, in sequential biaxial stretching, a method in which a uniaxially stretched film stretched in the longitudinal direction (vertical direction) is coated and then stretched in the transverse direction is particularly excellent. According to this method, film formation and antistatic layer coating can be performed at the same time, which is advantageous in terms of manufacturing costs.Since the coating is performed after coating, a thin and uniform coating is obtained, and the antistatic layer (A1) is Characteristics are easy to stabilize. In addition, by first coating the film before being stretched with a resin layer constituting the antistatic layer (A1), and then stretching the film and the antistatic layer at the same time, the base film and the antistatic layer (A1) can be coated. Another advantage is that it is easy to adhere firmly.

Biaxial stretching of the film involves holding the edges of the film with tenter clips and stretching it in the lateral direction, thereby restraining the film in the longitudinal/transverse directions and maintaining flatness without wrinkles during heat setting. It is possible to apply high temperature while keeping it in place. Therefore, since the heat treatment performed after coating can be performed at a high temperature that cannot be achieved by other methods, the film-forming properties of the antistatic layer are improved, and the antistatic layer (A1) and the film are tightly adhered. It tends to be easy.

In the case of the coating/stretching method, the coating liquid used is preferably an aqueous solution or an aqueous dispersion for reasons of handling, working environment, and safety, and preferably uses water as the main medium. Note that an organic solvent may be contained within the scope of the present invention.

The antistatic layer (A1) may be provided on either side of the layer (A), but may be provided on both sides. In particular, it is more preferable to have it on both sides because it has excellent adhesiveness with layer (B).

The antistatic layer (A1) is not particularly limited, and examples include conductive polymers, ionic liquids, ionic surfactants, and quaternary ammonium salts. Among these, preferred are conductive polymers, ionic liquids, and ionic antistatic agents such as ionic surfactants.

Examples of the conductive polymer include a polymer obtained by doping a compound made of thiophene or a thiophene derivative with another anionic compound, or a self-doped polymer (A1- Those containing 1) are preferred. These substances exhibit excellent electrical conductivity and are suitable. Examples include those obtained by polymerizing a compound represented by the following general formula (1) or (2) in the presence of a polyanion.

(In general formula (1), R ¹ and R ² each independently represent hydrogen, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group having 1 to 20 carbon atoms. .)

(In general formula (2), n represents an integer from 1 to 4.)

Examples of sources of polyanions used during polymerization include poly(meth)acrylic acid, polymaleic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, and the like. As a method for producing such a polymer, for example, a method as disclosed in JP-A-7-90060 can be adopted.

In the present invention, a preferred embodiment is a compound of the above general formula (2) in which n is 2 and polystyrene sulfonic acid is used as the source of the polyanion.

Further, some or all of these polyanions may be neutralized. As the base used for neutralization, ammonia, organic amines, and alkali metal hydroxides are preferable.

Examples of the self-doped polymer having an anionic group in a compound made of thiophene or a thiophene derivative include those in which the compound of the above general formula (1) or (2) is doped with an anionic group.

Further, it is also preferable that the antistatic layer (A1) contains the following (A1-2) and/or (A1-3).
(A1-2): One or more compounds selected from the group of glycerin, polyglycerin, alkylene oxide adducts to glycerin or polyglycerin, and polyalkylene oxide (A1-3): Polyurethane resin

Among the compounds (A1-2) selected from the group of glycerin, polyglycerin, glycerin or alkylene oxide adducts to polyglycerin, and polyalkylene oxides, containing polyglycerin, glycerin, or alkylene oxide adducts to polyglycerin. is more preferable.
Glycerin and polyglycerin are compounds represented by the following general formula (3).

In general formula (3), the compound where n=1 is glycerin, and the compound where n is 2 or more is polyglycerin. In the present invention, n is preferably 2 to 20, more preferably 2 to 10.

The alkylene oxide adduct to glycerin or polyglycerin has a structure in which alkylene oxide is addition-polymerized to the hydroxyl group of glycerin or polyglycerin represented by general formula (3).

Here, the structure of the alkylene oxide added to each hydroxyl group of the glycerin or polyglycerin skeleton may be different. Further, it is sufficient that the alkylene oxide or its derivative is added to at least one hydroxyl group in the molecule, and not all hydroxyl groups.

Preferred alkylene oxides to be added to glycerin or polyglycerin are ethylene oxide and propylene oxide. If the alkylene chain of the alkylene oxide becomes too long, the hydrophobicity becomes strong, making it difficult to disperse uniformly in the coating liquid, and the antistatic properties and transparency of the antistatic layer (A1) tend to deteriorate. Among them, ethylene oxide is preferred. Further, the number of additions is preferably such that the weight average molecular weight of the final adduct is 200 to 2,000, more preferably 300 to 800.

Preferred polyalkylene oxides are polyethylene oxide and polypropylene oxide. If the alkylene chain of the alkylene oxide becomes too long, the hydrophobicity becomes strong, making it difficult to disperse uniformly in the coating liquid, and the antistatic properties and transparency of the antistatic layer (A1) tend to deteriorate. More preferred is polyethylene oxide. The mass average molecular weight is preferably 200 to 2,000.

The polyurethane resin (A1-3) is not particularly limited as long as it has a urethane bond in its molecule, and water-dispersible or water-soluble ones are preferred.

In order to impart water dispersibility or water solubility, it is preferable to introduce hydrophilic groups such as hydroxyl groups, carboxyl groups, sulfonic acid groups, sulfonyl groups, phosphoric acid groups, and ether groups into the polyurethane resin. Among these hydrophilic groups, carboxyl groups and sulfonic acid groups are preferred from the viewpoint of coating film properties and adhesion.

The polyurethane resin (A1-3) is preferably one obtained by a reaction between a hydroxyl group and an isocyanate. As the hydroxyl group used as a raw material, polyols are preferably used, and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and acrylic polyols. Among them, polyether polyols, polyester polyols, and polycarbonate polyols are preferable. Among them, polyester polyols are preferred. Polyols are more preferred, and polyester polyols having an aromatic ring are even more preferred.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and the like.

Polyester polyols include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or acid anhydrides thereof. and polyhydric alcohols.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-Methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol , 2-methyl-2-propyl-1,3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2 , 5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2 -hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyl dialkanolamine, lactone diol and the like.

Examples of polycarbonate polyols include polycarbonate diols obtained by dealcoholization reaction from polyhydric alcohols and dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc., such as poly(1,6-hexylene) carbonate, poly(3- Examples include methyl-1,5-pentylene) carbonate.

The polyisocyanate compounds used to obtain the polyurethane resin (A1-3) include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, toridine diisocyanate, α, α, Aliphatic diisocyanates with aromatic rings such as α', α'-tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate , isophorone diisocyanate, dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl diisocyanate, and other alicyclic diisocyanates.

Furthermore, a chain extender may be used when synthesizing the polyurethane resin, and there are no particular restrictions on the chain extender as long as it has two or more active groups that react with isocyanate groups. , a chain extender having two hydroxyl groups or two amino groups can be mainly used.

Examples of the chain extender having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol, butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. Examples include glycols such as glycol.

Examples of the chain extender having two amino groups include aromatic diamines such as tolylene diamine, xylylene diamine, and diphenylmethane diamine, ethylene diamine, propylene diamine, hexane diamine, and 2,2-dimethyl-1,3-propane diamine. , 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine Aliphatic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, etc. can be mentioned.

Also preferably used is a method in which a carboxyl group is introduced into the urethane skeleton using dimethylolpropionic acid, dimethylolbutanoic acid, etc., and then neutralized with a basic compound to make the urethane hydrophilic.

The antistatic layer (A1) may contain a surfactant (A1-4) to improve coating properties. As the surfactant (A1-4), especially when one containing (poly)alkylene oxide, (poly)glycerin, or a derivative thereof in its structure is used, the antistatic properties of the resulting antistatic layer (A1) can be improved. It is more preferable because it does not inhibit it.

The coating liquid for forming the antistatic layer (A1) in the present invention may contain a crosslinking reactive compound, if necessary. Crosslinking-reactive compounds mainly improve the cohesiveness, surface hardness, scratch resistance, solvent resistance, and water resistance of the antistatic layer through crosslinking reactions with functional groups contained in other resins and compounds, or through self-crosslinking. be able to.
As the crosslinking-reactive compound, amino resins such as melamine, benzoguanamine, and urea, as well as isocyanate, oxazoline, epoxy, and glyoxal compounds are preferably used. Also included are polymer-type crosslinking-reactive compounds in which other polymer skeletons have reactive groups.

Furthermore, if necessary, binder resins other than the polyurethane resin (A1-3) can also be used in combination. Examples of the binder resin include polyether resin, polyester resin, acrylic resin, vinyl resin, epoxy resin, and amide resin. Each of these may have a substantially composite structure due to copolymerization or the like. Examples of the binder resin having a composite structure include acrylic resin grafted polyester, vinyl resin grafted polyester, and the like. By containing these resins, the strength of the antistatic layer obtained and the adhesion to the layer (A) tend to be improved.

The antistatic layer (A1) contains an antifoaming agent, a coating improver, a thickener, an organic lubricant, a mold release agent, an organic particle, an inorganic particle, an antioxidant, an ultraviolet absorber, a foaming agent, a dye, and a pigment. It may contain additives such as. In addition, when these additives contain (poly)alkylene oxide, (poly)glycerin, or derivatives thereof in their structure, they do not inhibit the antistatic properties of the resulting antistatic layer (A1). More preferred.

Among these, the antistatic layer (A1) preferably contains particles such as organic particles and inorganic particles for the purpose of blocking and improving slipperiness. The average particle diameter (D50) of the particles is preferably 1 μm or less, more preferably 0.5 μm or less, even more preferably 0.2 μm or less. Moreover, from the viewpoint of improving slipperiness more effectively, the thickness is preferably 0.005 μm or more, more preferably 0.01 μm or more. Examples of the particles include silica, alumina, kaolin, calcium carbonate, and organic particles, with silica being preferred.

The content of the polymer (A1-1) in the antistatic layer (A1) is preferably 0.5 mg/m ² or more, more preferably 1 mg/m ² or more, and 2 mg/m ² or more. It is more preferable that By setting the content of the polymer (A1-1) to 0.5 mg/m ² or more, the antistatic property becomes sufficient and adhesion between the laminates is easily suppressed. Moreover, it is preferably 15 mg/m ² or less, more preferably 9 mg/m ² or less, and even more preferably 5 mg/m ² or less. By setting the content of the polymer (A1-1) to 15 mg/m ² or less, it becomes less likely to be colored at low cost.

The content of the polymer (A1-1) relative to the nonvolatile components in the coating liquid forming the antistatic layer (A1) is preferably 1% by mass or more, more preferably 2% by mass or more, and 3% by mass or more. It is more preferably at least 4% by mass, particularly preferably at least 4% by mass. By setting the content of the polymer (A1-1) to 1% by mass or more, the strength of the antistatic layer (A1), the adhesion with the layer (A), and the antistatic performance tend to be sufficient. On the other hand, the content of the polymer (A1-1) is preferably 80% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, and 15% by mass or less. It is particularly preferable that there be. By setting the content to 80% by mass or less, deterioration of the appearance of the resulting laminate and blocking during production of the laminate are less likely to occur, which is preferable.

When the compound (A1-2) is included, the content of the compound (A1-2) relative to the nonvolatile components in the coating liquid is preferably 1% by mass or more, and 10% by mass or more from the viewpoint of antistatic performance and appearance. The content is more preferably 20% by mass or more, even more preferably 30% by mass or more. Further, it is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 55% by mass or less.

When containing a polyurethane resin (A1-3), the content of the polyurethane resin (A1-3) relative to the nonvolatile components in the coating liquid should be 2% by mass or more from the viewpoint of antistatic performance, strength, and water resistance. It is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 35% by mass or more. Further, it is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less.

When the surfactant (A1-4) is included, the content of the surfactant (A1-4) relative to the nonvolatile components in the coating liquid is 0.1% by mass or more from the viewpoint of antistatic performance and coatability. The content is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. Further, it is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

Note that the content ratios of (A1-1) to (A1-4) with respect to the nonvolatile components in the above-mentioned coating liquid can be treated as synonymous with the content ratios in the antistatic layer (A1).

The ionic antistatic agent is not particularly limited, and includes conventionally known ionic liquids and ionic surfactants.

Ionic liquids are salts that exist in liquid form and consist of anions and cations.
Examples of the anion of the ionic liquid include halogens such as tetrafluoroborate, hexafluorophosphate, chloride, tetrachloroaluminate, bromide, and iodide, imides such as trifluoromethanesulfonimide, and amides such as cyanamide and trifluoromethylsulfonylamide. , sulfates such as butyl sulfonate, methyl sulfate, ethyl sulfate, hydrogen sulfate, octyl sulfate, alkyl sulfate, phosphates such as butyl phosphate, nitrate, thiocyanate, acetate, aminoacetate, lactate, and the like. Among these, imide, amide, and sulfate are preferred, and imide and sulfate are more preferred, since they have excellent antistatic properties.

Examples of cations of ionic liquids include ammonium salts, imidazolium salts, phosphonium salts, pyridinium salts, pyrrolidinium salts, pyrrolinium salts, and triazonium salts. Among them, ammonium salts and imidazolium salts have excellent antistatic properties. Lium salts are preferred, and ammonium salts are more preferred.

Examples of ammonium salts include butyltrimethylammonium, ethyldiethylpropylammonium, 2-hydroxyethyl-triethylammonium, methyl-trioctylammonium, methyltrioctylammonium, tetrabutylammonium, tetraethylammonium, tetraheptylammonium, tributylmethylammonium, Examples include triethylmethylammonium and tris(2-hydroxy)methylammonium.

Examples of imidazolium salts include 1-allyl-3-methylimidazolium, 1-benzyl-3-methylimidazolium, 1,3-bis(cyanomethyl)imidazolium, 1,3-bis(cyanopropyl)imidazolium , 1-butyl-2,3-dimethylimidazolium, 4-(3-butyl)-1-imidazolium, 1-(3-cyanopropyl)-3-methylimidazolium, 1-ethyl-3-methylimidazolium , 1-butyl-3-methylimidazolium, 1-decyl-3-methylimidazolium, 1,3-diethoxyimidazolium, 1,3-dimethoxy-2-methylimidazolium, 1-hexyl-3-methylimidazolium 1-methyl-3-octylimidazolium, 1-methyl-3-propylimidazolium, and the like.

Examples of the phosphonium salt include tetrabutylphosphonium, tributylmethylphosphonium, trihexyltetradecylphosphonium, and the like.

Examples of pyridium salts include 1-butyl-3-methylpyridium, 1-butyl-4-methylpyridium, 1-butylpyridium, 1-ethylpyridium, 1-(3-cyanopropyl)pyridium, -methyl-4-propylpyridium and the like.

Examples of the pyrrolidinium salt include 1-butyl-1-methylpyrrolidinium, 2-methylpyrrolidinium, and 3-phenylpyrrolidinium.

Examples of pyrrolinium salts include 2-acetylpyrrolinium, 3-acetylpyrrolinium, and 1-(2-nitrophenyl)pyrrolinium.

Examples of ionic surfactants include sodium cholate, sodium deoxycholate, sodium glycolate, sodium taurocholate, sodium taurodeoxycholate, sodium N-lauroylsarcosine, hexadecyltrimethylammonium bromide, myristyltrimethylammonium bromide, and the like. can be mentioned.

As the above-mentioned ionic antistatic agent, one containing a sulfonic acid group is also preferable. As the sulfonic acid group-containing antistatic agent, in addition to known low-molecular-type sulfonic acid group-containing compounds, resins containing a sulfonic acid group component in the molecule such as polystyrene sulfonate, which is a polymeric antistatic agent, can be used. can be used. Among these, a polymer compound whose main component is polystyrene sulfonate, which is a polymer type antistatic agent, is preferable because it contains a large amount of hydrophilic sulfonic acid component.

Examples of resins containing sulfonic acid base components in the molecule include homopolymers such as sodium salts, potassium salts, lithium salts, ammonium salts, and phosphonium salts of polystyrene sulfonic acid, and acrylic monomers such as acrylic esters or methacrylic esters. Copolymers of various metal/amine salts of acrylamide methylpropanesulfonic acid and unsaturated monomers, etc., may be mentioned. The sulfonate may be a mixture of metal and amine salts.

The thickness of the antistatic layer (A1) is preferably 0.003 to 1 μm, more preferably 0.005 to 0.5 μm, as the thickness of the antistatic layer on the finally obtained laminate. , more preferably 0.01 to 0.1 μm. By setting the thickness to 0.003 μm or more, good antistatic performance can be easily obtained, and by setting the thickness to 1 μm or less, problems such as deterioration of appearance and blocking during production of the laminate are less likely to occur.

When providing the antistatic layer (A1) on the layer (A), the process of providing the antistatic layer (A1) or the process of imparting surface roughness such as sandblasting may be performed first, but uniform roughness may be performed. From the viewpoint of securing the antistatic layer (A1), it is preferable to first perform the step of imparting surface roughness, and then perform the step of providing the antistatic layer (A1).

<Layer (B)>
Layer (B) is a layer mainly composed of resin (b) having a storage modulus of 100 MPa or less at 23°C. The storage modulus of the resin (b) is preferably 70 MPa or less, more preferably 50 MPa or less, from the viewpoint of followability to the molded body during press molding, adhesion, and surface tackiness of the layer (B). , more preferably 30 MPa or less, particularly preferably 10 MPa or less. Moreover, it is preferably 0.1 MPa or more, more preferably 0.5 MPa or more, and still more preferably 1 MPa or more.
The resin (b) having a storage modulus of 100 MPa or less at 23°C is not particularly limited, and examples include olefin elastomer resins, styrene elastomer resins, polyester elastomer resins, urethane resins, epoxy resins, and fluorine resins. Examples include elastomer resins, but silicone resins are preferred because of their excellent heat resistance, electrical properties such as insulation, and mold releasability. The silicone resin is not particularly limited and conventionally known ones can be used, but a silicone elastomer resin having a siloxane skeleton represented by the following general formula (4) is particularly preferable, and it can be cured to form the layer (B). More preferred. In the following general formula (4), in addition to polydimethylsiloxane in which all R's in the formula are methyl groups, a part of the methyl groups is one type of other alkyl group, vinyl group, phenyl group, fluoroalkyl group, etc. Alternatively, various polydimethylsiloxanes substituted with two or more types can also be selected as appropriate.

Further, it is also preferable that the silicone resin is a silicone resin whose main component is polydimethylsiloxane containing a vinyl group, particularly a silicone elastomer resin, from the viewpoint of adjusting the compression set. When containing a vinyl group, the content of the vinyl group based on the total amount of polydimethylsiloxane is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, and 0.5 mol%. It is more preferably at least 1 mol %, particularly preferably at least 1 mol %. When the content of vinyl groups is 0.05 mol%, the crosslinking density of the silicone elastomer resin can be easily adjusted, and a silicone elastomer resin having a desired compression set can be obtained. On the other hand, the content of vinyl groups is preferably 5 mol% or less, more preferably 4 mol% or less, even more preferably 3 mol% or less, and particularly preferably 2 mol% or less. . A content of 5 mol % or less is preferable because the silicone elastomer resin will not be excessively cured.

Examples of methods for curing the silicone elastomer resin include a method of adding a curing catalyst, a method of heating at high temperature, a method of adding a crosslinking agent, and a method of crosslinking by radiation irradiation. Among these, curing by radiation is preferable. When curing by radiation, there is no concern that heat resistance and light resistance reliability will be impaired due to residues of catalysts or crosslinking agents. Further, since no heat is applied during curing, there is no fear of thermal deterioration, which is preferable.

Examples of the radiation include electron beams, X-rays, and gamma rays. These radiations are widely used industrially, are easily available, and are energy efficient methods. Among these, it is preferable to use gamma rays from the viewpoint of almost no absorption loss and high transparency.

The irradiation dose of γ-rays can be appropriately selected and determined depending on the type of resin, the amount of crosslinking groups, and the type of radiation source. For example, the irradiation dose of gamma rays is preferably 20 kGy or more, more preferably 50 kGy or more, and even more preferably 60 kGy. When the irradiation dose is 20 kGy or more, the silicone elastomer resin can be sufficiently cured, and as a result, a desired compression set can be obtained. On the other hand, the irradiation dose of gamma rays is preferably 150 kGy or less, more preferably 120 kGy or less, and even more preferably 100 kGy or less. If the irradiation dose is 150 kGy or less, the increase in low molecular weight components due to decomposition reactions tends to be easily suppressed.

The hardness of the layer (B) obtained by curing in this manner is preferably 3 or more, more preferably 10 or more in Type A durometer hardness measured based on JIS K6253-3:2012. It is preferably 20 or more, and more preferably 20 or more. On the other hand, it is preferably 90 or less, more preferably 80 or less, and even more preferably 70 or less. When the hardness is 3 or more, the surface tackiness of the layer (B) is suppressed, and the handleability of the resulting laminate tends to be improved. On the other hand, if the hardness is 90 or less, followability and adhesion to a molded product during press molding etc. are likely to be improved.
If the hardness of layer (B) cannot be directly measured, it is sufficient to measure the type A durometer hardness of the raw resin used for layer (B) cured under similar curing conditions. do.

Methods for adjusting the type A durometer hardness of layer (B) include, for example, the method of adjusting the amount of radiation irradiation described above, and the method of adjusting the amount of filler such as silica added as a reinforcing material to the silicone elastomer resin. Preferred examples include a method of appropriately selecting the type of silicone elastomer resin as a raw material, specifically a method of adopting a resin having phenyl groups and adjusting the content of phenyl groups, and a method of adjusting the amount of radiation irradiation. is simple and more preferable.

Furthermore, the silicone elastomer resin that is preferably used has functionality as an elastomer, in addition to reinforcing fillers such as fumed silica, precipitated silica, diatomaceous earth, and quartz powder, various processing aids, and heat resistance improvers. It may contain various additives. Examples of the functional additive include a flame retardant agent, a heat dissipating filler, and a conductive filler.

Commercially available products can also be used as such silicone elastomer resins. As commercially available products, a millable silicone compound manufactured by Shin-Etsu Chemical Co., Ltd. and a millable silicone rubber manufactured by Momentive Performance Materials can be used.

Layer (B) contains additives such as ultraviolet absorbers, light stabilizers, antioxidants, plasticizers, nucleating agents, lubricants, pigments, and dyes, as well as storage elasticity at 23°C, within a range that does not impair the effects of the present invention. It may contain a resin having a modulus of more than 100 MPa.

The surface roughness of at least one side of the layer (B) preferably satisfies either or both of the following requirements (iii) and (iv).
(iii) Ten point average roughness (Rz) is 0.3 μm or more (iv) Arithmetic average roughness (Ra) is 0.05 μm or more

Rz is more preferably 0.5 μm or more, even more preferably 1 μm or more, particularly preferably 2 μm or more, and most preferably 3 μm or more. It is preferable that Rz is 0.3 μm or more because when the laminates of the present invention are stacked together, the convex portions come into point contact, which tends to suppress adhesion of the laminates to each other, resulting in excellent handling properties. In addition, it is preferable because the contact state with the molded body, press plate, or mold becomes good and positioning becomes easy, and the productivity and dimensional stability of the molded body tend to be improved. In particular, it is preferable that during press molding, sufficient slipperiness between the laminate and the molded body is ensured, making positioning easier. Further, Rz is preferably 10 μm or less, more preferably 8 μm or less, even more preferably 7 μm or less, and particularly preferably 6 μm or less. It is preferable that Rz is 10 μm or less, since the handling property when disposed in a molded body, a press plate, or a mold tends to be good, and the dimensional stability of the press-formed body tends to be good.

For the same reason, the arithmetic mean roughness (Ra), maximum height roughness (Ry), and average spacing of unevenness (Sm) of at least one surface of the layer (B) are preferably in the following ranges.
Ra is preferably 0.05 μm or more, more preferably 0.1 μm or more, even more preferably 0.3 μm or more, particularly preferably 0.4 μm or more, and 0.5 μm or more. Most preferably. Further, Ra is preferably 5 μm or less, more preferably 4 μm or less, even more preferably 3 μm or less, particularly preferably 2 μm or less, and most preferably 1.5 μm or less.

Ry is preferably 0.4 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, particularly preferably 3 μm or more, and most preferably 3.5 μm or more. . Further, Ry is preferably 10 μm or less, more preferably 9 μm or less, even more preferably 8 μm or less, and particularly preferably 7 μm or less.

Sm is preferably 70 μm or less, more preferably 60 μm or less, even more preferably 55 μm or less, and particularly preferably 50 μm or less. Further, Sm is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more.

Examples of methods for obtaining the layer (B) having the above-mentioned surface roughness include sandblasting, shotblasting, etching, engraving, embossing roll transfer, embossing belt transfer, embossing film transfer, surface crystallization, etc. Various methods can be used. In particular, a method using an embossed film transfer using a cover sheet is preferred because it protects the laminate from external forces and contamination and improves handling properties during transportation, winding, storage, and use of the laminate.

The cover sheet is preferably an embossed film, and by transferring the cover sheet to the layer (B), a layer (B) with a desired surface roughness can be obtained.

As a preferable cover sheet, one that is itself non-adhesive (the sheets do not stick to each other) and has high strength is preferably used. Specifically, a plastic film such as polyethylene terephthalate (PET) or a metal foil such as aluminum foil or copper foil is suitable. For the purpose of improving releasability, it is also possible to provide a release layer of fluorine or the like on the surface.

Furthermore, it is important that the layer (B) has irregularities for transferring the desired surface roughness. As a method for forming surface irregularities on the cover sheet, conventionally known blasting methods and chemical methods can be used.

The thickness of the cover sheet is determined as appropriate depending on its material, purpose of use, etc. For example, the thickness of the cover sheet is approximately 5 to 500 μm for a plastic film such as PET film, and 5 to 500 μm for a metal foil such as aluminum foil or copper foil. The thickness is preferably about 100 μm.

In addition, when a silicone elastomer resin is used as the resin (b) and the layer (B) is formed by crosslinking the resin, for example, layer (A)/silicone elastomer resin layer (B) before crosslinking/cover sheet. It is preferable to stack the layers in order and irradiate the stacked layers with radiation to crosslink and harden them, from the viewpoint of fixing and maintaining the shape of the layer (B) before crosslinking and from the viewpoint of productivity.

The thickness of layer (B) is preferably 10 μm or more, more preferably 30 μm or more, even more preferably 50 μm or more, particularly preferably 60 μm or more, and most preferably 70 μm or more. preferable. When the thickness of the layer (B) is 10 μm or more, it is easy to obtain rubber elastic properties as a laminate, and the cushioning properties and followability during press molding etc. are likely to be good. On the other hand, the thickness is preferably 1000 μm or less, more preferably 750 μm or less, still more preferably 500 μm or less, particularly preferably 300 μm or less, from the viewpoint of use, cost, and thickness accuracy of the molded product. In the present invention, the term "thickness" refers to the average thickness when thicknesses are measured at ten arbitrary points.

In the present invention, the resin (a) having a storage modulus of 1000 MPa or more at 23°C is a polyester resin, and the resin (b) having a storage modulus of 100 MPa or less at 23°C is a silicone resin, particularly a silicone elastomer resin. In this case, it is preferable to have an undercoat layer and/or a thin film layer between the layer (A) and the layer (B) in this order from the layer (A) side, from the viewpoint of improving the adhesion and adhesion between the two. When the layer (A) has an antistatic layer (A1), it is preferable that the antistatic layer (A1)/layer (A)/undercoat layer and/or thin film layer/layer (B) be laminated in this order. Surprisingly, when the antistatic layer (A1) is present between the layer (A) and the layer (B), specifically, layer (A)/antistatic layer (A1)/undercoat layer and/or Alternatively, the layer (A ) and the layer (B) were found to have better adhesion and adhesion.

<Undercoat layer>
The undercoat layer preferably contains an amorphous polymer as a main component. The amorphous polymer is not particularly limited as long as it can be applied uniformly to the layer (A), and may be appropriately selected from substantially non-crystalline polymers such as polyurethane resin, acrylic resin, and amorphous polyester resin. Just choose.

Specific examples include polyurethane resins made by increasing the molecular weight of polyester resins and/or polyether resins into linear chains with urethane bonds, acrylic resins made from copolymers of acrylic acid and/or methacrylic esters, acid components, or glycols. Examples include copolyester resins whose components are composed of two or more types of monomers. Since these amorphous resins are applied to a thin film, they are usually used diluted with an organic solvent or emulsified or solubilized in water to adjust the concentration to an appropriate level.

The undercoat layer may have a crosslinked structure for the purpose of improving heat resistance and solvent resistance. In this case, the amorphous polymer has a carboxyl group, hydroxyl group, or amino group in the main chain or side chain. It has iso-crosslinkable functional groups, and the crosslinking agent is appropriately selected from polyisocyanates, melamine, polyfunctional epoxy resins, metal compounds, etc. Further, in addition to the above-mentioned crosslinking agent, the coating liquid may contain a leveling agent such as a surfactant, an antiblocking agent such as silica, a thickener, and the like.

The thickness of the undercoat layer after drying is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more. If the thickness of the undercoat layer is 0.01 μm or more, it is preferable because the coating thickness can be easily adjusted and the adhesiveness with a thin film layer containing a silicone resin described below is also good. Further, the thickness after drying is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. If the thickness after drying is 5 μm or less, the undercoat layer can be applied more easily, which is preferable.

Moreover, as a coating method, a known method can be applied depending on the coating liquid used. In order to improve the leveling properties and adhesion of the coating liquid, the coated surface of the layer (A) may be subjected to a surface treatment such as corona treatment in advance.

<Thin film layer>
The thin film layer preferably contains silicone resin as a main component. Examples of silicone resins include those that form a crosslinked film by heating or UV irradiation after coating, and those that form a crosslinked film simultaneously when layer (B) is crosslinked if layer (B) is a silicone elastomer resin. Can be mentioned.

Examples of silicone resins that can be used in the thin film layer include addition type silicone resins, condensation type silicone resins, UV-curable silicone resins, and the like. Examples of addition-type silicone resins include those obtained by using polydimethylsiloxane containing vinyl groups as a base polymer, blending polymethylhydrogensiloxane as a crosslinking agent, and curing the mixture in the presence of a platinum catalyst. Examples of the type silicone resin include those obtained by using polydimethylsiloxane containing a silanol group at the terminal as a base polymer, blending polymethylhydrogensiloxane as a crosslinking agent, and curing by heating in the presence of an organotin catalyst.

Examples of UV-curable silicone resins include those whose base polymer is polydimethylsiloxane containing an acryloyl group or methacryloyl group, those whose base polymer is polydimethylsiloxane containing a mercapto group and a vinyl group, and the above-mentioned addition type silicone resins. Examples include compounds in which a photopolymerization initiator is blended with a base polymer of polydimethylsiloxane containing an epoxy group that cures by a cationic curing mechanism, and cured by irradiation with ultraviolet rays.

A coating solution is prepared by appropriately adding a solvent to the above-mentioned silicone resin compound, and the coating solution is coated on the polyester resin layer (A) to form a thin film layer.

The coating liquid preferably contains an additive such as a silane coupling agent for the purpose of increasing affinity with the undercoat layer. A silane coupling agent that satisfies this purpose is a compound represented by the general formula _YRSiX3 , where Y is an organic functional group such as a vinyl group, epoxy group, amino group, or mercapto group, and R is an alkylene group such as methylene, ethylene, or propylene. , X is a hydrolyzable functional group such as a methoxy group or an ethoxy group, or an alkyl group. Specific compounds include, for example, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidylpropyltrimethoxysilane, γ-glycidylpropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N- Examples include β(aminoethyl)-γ-aminopropylmethyldimethoxysilane and γ-mercaptopropyltrimethoxysilane.

The thickness of the thin film layer after solvent drying is preferably 0.01 μm or more, more preferably 0.03 μm or more, and even more preferably 0.05 μm or more. When the coating thickness is 0.01 μm or more, a cured film with a uniform thickness can be obtained, and sufficient adhesive strength with layer (B) can be easily obtained. Furthermore, since the silicone resin having the above composition generally does not have a very strong film strength, cohesive failure tends to occur in the resin layer (B) when evaluating the peel strength of the laminate, but if the thickness is 1 μm or less, Cohesive failure of the layer (B) is suppressed, and it tends to be easy to obtain sufficient strength as a laminate. From this viewpoint, the thickness of the thin film layer after solvent drying is more preferably 0.7 μm or less, and even more preferably 0.5 μm or less.

The coating method for the thin film layer is not particularly limited as long as it can form a thin film with high precision like the undercoat layer, and any known coating method can be applied.

<Friction coefficient>
In the laminate of the present invention, the coefficient of static friction between the layer (A) side surface of one laminate and the layer (B) side surface of the other laminate is 2.1 or less. This is preferable from the viewpoint of handling properties such as peelability between bodies and positioning. The static friction coefficient is more preferably 1.8 or less, more preferably 1.5 or less, even more preferably 1.3 or less, particularly preferably 1.2 or less, and 1 or less. Most preferably. The coefficient of static friction is preferably 0.3 or more, more preferably 0.5 or more, and even more preferably 0.7 or more from the viewpoint of handling properties such as transportation and positioning of the laminate. preferable.

Further, in the laminate of the present invention, the coefficient of dynamic friction between the layer (A) side surface of one laminate and the layer (B) side surface of the other laminate is 1.8 or less. This is preferable from the viewpoint of handling properties such as peelability and positioning of the laminates. The coefficient of dynamic friction is more preferably 1.5 or less, even more preferably 1.3 or less, particularly preferably 1.1 or less, particularly preferably 0.9 or less, and particularly preferably 0.8 or less. Most preferably. The dynamic friction coefficient is preferably 0.2 or more, more preferably 0.4 or more, and even more preferably 0.6 or more from the viewpoint of handling properties such as transportation and positioning of the laminate. .
In addition, as mentioned above, when the antistatic layer (A1) is provided to the layer (A), the surface on the side of the antistatic layer (A1) of one laminate and the layer (A1) of the other laminate B) Refers to the coefficient of friction with the side surface.

<Relative dielectric constant>
In the present invention, the effect of the present invention becomes remarkable when the dielectric constant difference between the layer (A) and the layer (B) is 0.15 or more. The adhesion of the laminates, which is a problem of the present invention, that is, the decrease in the releasability of the two, is thought to be caused by static electricity generated due to the dielectric constant difference between the layer (A) and the layer (B). It is. For these reasons, the effects of the present invention are obtained when the dielectric constant difference between the layer (A) and the layer (B) is 0.2 or more, further 0.23 or more, particularly 0.25 or more. becomes noticeable.

<Laminated structure>
The layer structure of the laminate of the present invention is not particularly limited, but from the viewpoint of easily obtaining the effects of the present invention, a structure in which the layer (A) is the outermost layer is preferred, and in particular, a structure in which the layer (A) and the layer (B) are It is preferable that both of these be the outermost layers. Examples include a two-layer structure of layer (A)/layer (B), and a structure in which another resin layer is provided between layer (A) and layer (B). Although other resin layers are not particularly limited, for example, it is preferable to include the above-mentioned undercoat layer, thin film layer, and antistatic layer (A1) as appropriate.
Further, as described above, it is also preferable that the antistatic layer (A1) is laminated on the side of the layer (A) opposite to the side on which the layer (B) is laminated, and in this case, the antistatic layer ( It is preferable that A1) be the outermost layer.

<Manufacturing method>
The method for manufacturing the laminate of the present invention is not particularly limited, and conventionally known methods can be employed. For example, a layer (A) may be produced, a layer (B) may be produced separately, and these may be laminated, or a layer (A) may be produced, and a layer (B) may be stacked on this layer (A). Alternatively, layer (B) may be prepared, layer (A) is formed on layer (B), and layer (A) may be integrated. Layer (A) and layer (B) may be integrated. ) may be laminated and integrated while producing them.

The process of producing layer (A) and layer (B) includes a method of melt-kneading raw resin and extruding it using a single-screw or twin-screw extruder.
Layer (A) and layer (B) can be laminated by coextrusion, extrusion lamination, heat lamination, dry lamination, or the like. Specifically, the block layer (A) and the layer (B) may be simultaneously kneaded and co-extruded using a feed block method or a multi-manifold method, etc. to form a single layer, or the layer (A) and the layer (B) may be formed. A method may also be used in which the layers (A) and (B) are obtained by performing the above steps separately, and then the layers are laminated.

In the case of coextrusion, a laminate can be produced by combining resins of layer (A) and layer (B) using a plurality of extruders through a feed block or a multi-manifold die.

In the case of extrusion lamination, the resin (b) is extruded through a T-die, I-die, etc. using a single-screw or twin-screw extruder, and then layer (B) is formed using a roll method, tenter method, tubular method, etc. A monolayer body is obtained. Subsequently, when extruding the resin (a) from a T-die, I-die, etc. using a single-screw or twin-screw extruder, the layer (A) is laminated at the same time as casting to obtain the laminate of the present invention. be able to.

In the case of thermal lamination or dry lamination, the resin (b) is extruded from a T-die, I-die, etc. using a single-screw or twin-screw extruder to obtain a monolayer body serving as the layer (B). Further, a layer (A) made of resin (a) is produced using a similar method. Subsequently, the layer (A) and the layer (B) are laminated under heating or by disposing an adhesive layer between the layers to obtain the laminate of the present invention.

In the present invention, the resin (a) having a storage modulus of 1000 MPa or more at 23°C is a polyester resin, and the resin (b) having a storage modulus of 100 MPa or less at 23°C is a silicone resin, particularly a silicone elastomer resin. In this case, for example, the following method can be used.

As a specific manufacturing method, it is preferable to provide an undercoat layer, a thin film layer, and a layer (B) in this order on at least one side of the layer (A), and to cure the layer (B) by irradiation with gamma rays.

First, a coating liquid as an undercoat layer is applied to at least one side of the layer (A), and then dried and further thermally crosslinked as necessary to form an undercoat layer. As a coating method, a known method suitable for the coating liquid can be applied, and it may be applied to a plastic sheet or film formed in a separate process, or it can be applied directly to an unstretched sheet of the plastic sheet or film. An undercoat layer may be formed by applying a liquid and then stretching it. Further, the coated surface may be subjected to surface treatment such as corona treatment in advance in order to improve the leveling properties and adhesion of the coating liquid.

Next, a thin film layer, preferably containing a silicone resin, is applied onto the undercoat layer. As a coating method, a known method can be used as in the case of the undercoat layer described above.

Furthermore, layer (B) is formed by the following method. When the resin (b) is a silicone elastomer resin, the layer (B) made of the silicone elastomer resin is first laminated on the thin film layer in an uncrosslinked state. As a lamination method, the uncrosslinked silicone elastomer resin may be formed into a sheet by extrusion molding, injection molding, calendar molding, press molding, etc. and then laminated on a thin film layer, or a thin film may be formed by a known coating method. A method of forming a film directly on the layer may also be used.

Then, the laminate of the present invention can be obtained by curing with radiation. As the radiation, gamma rays, electron beams, X-rays, etc. can be suitably used.

As described above, in the present invention, it is preferable to use a silicone resin, particularly a silicone elastomer resin, as the layer (B), and to cure the silicone elastomer resin layer (B) by irradiation with gamma rays. From the viewpoint of obtaining a desired compression set in the silicone elastomer resin layer (B), the γ-ray irradiation dose is preferably 20 kGy or more, more preferably 50 kGy or more, even more preferably 60 kGy or more, and 150 kGy. It is preferable to irradiate at less than 120 kGy, more preferably at most 120 kGy, even more preferably at most 100 kGy.

In addition, in selecting the irradiation dose, it is necessary to take into consideration the crosslinking density of the silicone elastomer as well as the radiation resistance of the plastic film used as the base material. In this regard, when the layer (A) is made of polyester resin, it is a base material that generally has excellent resistance to radiation and is extremely suitable for the purpose of the present invention.

As mentioned above, the laminate of the present invention has the problem that the laminates are difficult to stick to each other, so that when the laminates are taken out one by one for use, multiple sheets are not taken out, and the laminates are difficult to stick to each other and peel off. Since it does not occur, it has excellent workability and handling during press molding. In addition, when the mold or press plate is opened after press molding and the product is taken out, problems such as the laminate remaining attached to the mold or press plate side are less likely to occur, so using a mold or press plate is less likely to occur. It can be suitably used for press molding.
Specifically, a press molding method in which a molded body is placed between the laminates and molded so that the layer (B) side is the molded body side can be suitably used.

The laminate of the present invention has excellent properties as a mold release material during press molding, so it can be used, for example, in display/touch panel related product parts such as ICs, semiconductors, and passive components incorporated in electrical and electronic products, and LED lighting. It can be suitably used for manufacturing molded bodies such as product members.

Storage modulus, dielectric constant, type A durometer hardness, surface roughness of the obtained laminate, coefficient of friction, and stacking test of the laminate were conducted in the following manner.

<Evaluation method>
Storage modulus:
Using a viscoelastic spectrometer "DVA-200 (manufactured by IT Keizai Control Co., Ltd.)", the temperature range was -100 to 250°C, the heating rate was 3°C/min, and the vibration frequency was 1Hz, in accordance with JIS K7244-4:1999. The storage elastic modulus at 23° C. was obtained when measured under the conditions of a strain of 0.1%, a distance between chucks of 25 mm, and a tensile method. In addition, regarding the biaxially stretched PET film, measurements were performed in the MD direction of the film.

Relative permittivity:
Hewlett Packard 4284A (electrode part is Agilent technology Dielectric test fixture 16451B) according to JIS C2138:2007, temperature 20°C, relative humidity 65%, applied voltage 1V, frequency 1MHz Measured under the following conditions.

Type A durometer hardness:
It was measured using a type A durometer (manufactured by Kobunshi Keiki Co., Ltd.) based on JIS K6253-3:2012.

Surface roughness:
The surface roughness of the front and back surfaces of the laminate obtained by the method described below was measured using a Surfcorder ET4000A (manufactured by Kosaka Institute Co., Ltd.). In Table 1, "-" for Sm means that the measured value exceeds 200 μm.

Coefficient of friction:
Two test pieces were cut out from the laminate obtained by the method described below. Referring to JIS K7125:1999, the layer (A) side surface of one test piece and the layer (B) side surface of the other test piece were kept in contact for 15 seconds before starting the test, and then the following conditions were applied. It was measured with
Equipment: Slip tester manufactured by Intesco Sliding piece: Total mass 200 g (contact area is a square with a side of 63 mm)
Contact area: ^40cm2
Test speed: 100mm/min
Temperature: 23℃±2℃
Relative humidity: 50% ± 10%

Overlap test:
A 10 cm x 10 cm test piece was cut out from the laminate obtained by the method described below, and 10 test pieces were stacked with the front and back sides in the same direction. After 30 minutes, one of the four corners of the top 10 stacked test pieces was picked up by hand and evaluated. The case where only the lifted test piece was taken out was evaluated as "○", and the case where the lower test piece was also attached and multiple pieces were lifted and taken out was evaluated as "x".

In addition, as an example of using PET as the resin (a) and silicone elastomer resin as the resin (b), a measurement sample prepared under the following conditions was used, but the method for preparing the measurement sample is limited to these. It's not a thing.

<Sample for storage modulus and dielectric constant measurement>
Layer (A):
The biaxially stretched PET film used for producing the laminate was used as it was.
For the sample for measuring the dielectric constant, a 45 mmφ electrode was formed from aluminum using a vacuum evaporation machine (VTR-350M, manufactured by ULVAC Kiko Co., Ltd.).

Layer (B):
The silicone elastomer resin used as a raw material is supplied between two biaxially stretched PET films (Diafoil T-100 manufactured by Mitsubishi Chemical Corporation) that are supplied along two calenders with a diameter of 100 mm, and the roll temperature is A bank was formed on the roll at 80° C. to create a laminate of PET film/silicone elastomer resin layer (thickness 100 μm)/PET film. The resulting laminate was irradiated with gamma rays at an absorbed dose of 50 kGy to crosslink the silicone elastomer resin, and then the PET films on both sides were peeled off to obtain a measurement sample.
Aluminum foil with a thickness of 10 μm and a diameter of 45 mm was directly attached to the sample for measuring the dielectric constant, and electrodes were formed thereon.

<Sample for type A durometer hardness measurement>
The silicone elastomer resin used as a raw material was sandwiched between two biaxially stretched PET films (Diafoil T-100 manufactured by Mitsubishi Chemical Corporation) and press-molded at 200°C to create a sheet of silicone elastomer resin with a thickness of 10 mm. The obtained sheet was irradiated with gamma rays at an absorbed dose of 50 kGy to obtain a measurement sample.

Details of the laminates of Examples are shown below, but the present invention is not limited by these. The laminates of Examples and Comparative Examples were manufactured by the method described below.

Example 1:
<Production of PET film having undercoat layer and thin film layer>
As layer (A), a corona-treated 100 μm thick biaxially stretched polyethylene terephthalate (PET) film (Diafoil T-100 manufactured by Mitsubishi Chemical Corporation, storage modulus 4950 MPa, dielectric constant 3.16) was used. , Sandblasting was performed on the side of the PET film that had not been subjected to corona treatment.

14 parts by mass of amorphous polyester resin (Vylon 240, manufactured by Toyobo Co., Ltd.), 2 parts by mass of polyisocyanate (Coronate L, manufactured by Tosoh Corporation), and a solvent (MEK/toluene = 1/4 (mass ratio)) ) It was diluted to 84 parts by mass to prepare a coating solution for an undercoat layer.
The above coating solution was applied to the corona-treated surface of the above PET film using a bar coater so that the thickness after drying would be 1.0 μm, and the solvent was dried and crosslinked in a gear oven at 100°C for 10 minutes. An undercoat layer was formed.

20 parts by mass of a condensation type silicone resin composition (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name SRX290) and 1.2 parts by mass of a curing agent (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name SRX242C) were mixed with a solvent ( Toluene) was diluted to 78.8 parts by mass to obtain a coating solution for a thin film layer. This coating solution was applied onto the undercoat layer using a bar coater so that the thickness after drying was 0.2 μm, and dried and crosslinked in a gear oven at 100°C for 10 minutes to form a thin film layer. A PET film of PET/undercoat layer/thin film layer was obtained.

<Manufacture of laminate>
As a raw material for layer (B), a millable silicone elastomer resin (manufactured by Momentive Performance Materials, TSE2571-5U, storage modulus 3.5 MPa, dielectric constant 2.87, type A durometer hardness 55) was used. The silicone elastomer resin is placed between the thin film layer of the PET film fed along two calenders with a diameter of 100 mm and the biaxially stretched PET film (Ra=0.95 μm) which has been chemically treated as a cover sheet. was supplied and a bank was formed on the roll at a roll temperature of 80°C to produce a laminate of PET film/silicone elastomer resin layer/cover sheet.
The resulting laminate was irradiated with gamma rays at an absorbed dose of 50 kGy to crosslink the silicone elastomer resin, thereby producing a laminate (layer (A)/ Undercoat layer/thin film layer/layer (B)/cover sheet) was obtained. The thickness of layer (B) was 100 μm.
The cover sheet was peeled off from this laminate to obtain a laminate of layer (A)/undercoat layer/thin film layer/layer (B) for evaluation.
Table 1 shows the results of evaluating the obtained laminate using the above method.

Example 2:
A laminate was obtained in the same manner as in Example 1, except that the cover sheet was replaced with a biaxially stretched PET film (Diafoil T-100 manufactured by Mitsubishi Chemical Corporation) that was not subjected to chemical treatment. Ta.
Table 1 shows the results of evaluating the obtained laminate using the above method.

Comparative example 1:
A laminate was obtained in the same manner as in Example 1 except that the PET film used in Example 1 was not subjected to sandblasting.
Table 1 shows the results of evaluating the obtained laminate using the above method.

Comparative example 2:
A laminate was obtained in the same manner as in Example 1, except that the PET film used in Example 1 was not subjected to sandblasting and the cover sheet was replaced with a biaxially stretched PET film that was not subjected to chemical treatment.
Table 1 shows the results of evaluating the obtained laminate using the above method.

In Examples 1 and 2, in which the surface roughness on the layer (A) side was within the desired range, good results were obtained in the stacking test.
On the other hand, in Comparative Examples 1 and 2 where the roughness on the layer (A) side was small, a plurality of laminates were taken out in the stacking test.

Based on the above results, it is considered that the following embodiments can also achieve the same effects as the above embodiments.

(Example 1, 2)
Examples 1 and 2 were the same as Examples 1 and 2 except that KE-581-U (storage modulus 6.0 MPa, type A durometer hardness 80) manufactured by Shin-Etsu Silicone Co., Ltd. was used as the millable silicone elastomer resin. A laminate manufactured by the method.

(Example 3, 4)
In Examples 1 and 2, TSE2913-U manufactured by Momentive Performance Materials (storage modulus 1.2 MPa, dielectric constant 2.69, type A durometer hardness 20) was used as the millable silicone elastomer resin. is a laminate manufactured by the same method as in Examples 1 and 2.

(Example 5, 6)
Example 1 except that in Examples 1 and 2, an antistatic layer using an anionic antistatic agent was provided as an antistatic layer (A1) on the sandblasted surface of the PET film used for producing the laminate. , a laminate manufactured by the same method as 2.
The method for measuring the surface resistivity on the antistatic layer (A1) side is as follows, and the surface roughness of the layer (A) is measured as the surface roughness of the antistatic layer (A1).

Surface resistivity:
A test piece was cut out from the obtained laminate, placed in a test box Resistivity Chamber R12702A/B, and measured at a voltage of 500V and a temperature using a digital ultra-high resistance/microcurrent meter R8340/8340A (both manufactured by ADC). Surface resistivity is measured in accordance with JIS K6911:2006 (5.13) under conditions of 23° C. and 50% humidity.

(Example 7, 8)
In Examples 5 and 6 above, the same method as in Examples 5 and 6 was used except that KE-581-U manufactured by Shin-Etsu Silicone Co., Ltd. (storage modulus 6.0 MPa, type A durometer hardness 80) was used as the millable silicone elastomer resin. A laminate manufactured by.

(Example 9, 10)
In Examples 5 and 6 above, except for using TSE2913-U manufactured by Momentive Performance Materials (storage modulus 1.2 MPa, dielectric constant 2.69, type A durometer hardness 20) as the millable silicone elastomer resin. is a laminate produced in the same manner as in Examples 5 and 6.

Claims (13)

A layer (A) whose main component is a resin (a) whose storage modulus at 23°C is 1000 MPa or more; and a layer (B) whose main component is a resin (b) whose storage modulus at 23°C is 100 MPa or less. A laminate comprising: at least the surface roughness of the side of the layer (A) on which the layer (B) is not laminated satisfies either or both of the following requirements (i) and (ii): A laminate that satisfies the following and has a static friction coefficient of 2.1 or less between a surface on the layer (A) side of one laminate and a surface on the layer (B) side of the other laminate. .
(i) 10-point average roughness (Rz) is 0.3 μm or more (ii) Arithmetic average roughness (Ra) is 0.05 μm or more A layer (A) whose main component is a resin (a) whose storage modulus at 23°C is 1000 MPa or more; and a layer (B) whose main component is a resin (b) whose storage modulus at 23°C is 100 MPa or less. A laminate comprising: at least the surface roughness of the side of the layer (A) on which the layer (B) is not laminated satisfies either or both of the following requirements (i) and (ii): A laminate which satisfies the following and has a dynamic friction coefficient of 1.8 or less between a surface on the layer (A) side of one laminate and a surface on the layer (B) side of the other laminate .
(i) 10-point average roughness (Rz) is 0.3 μm or more (ii) Arithmetic average roughness (Ra) is 0.05 μm or more A layer (A) whose main component is a resin (a) whose storage modulus at 23°C is 1000 MPa or more; and a layer (B) whose main component is a resin (b) whose storage modulus at 23°C is 100 MPa or less. A laminate comprising: at least the surface roughness of the side of the layer (A) on which the layer (B) is not laminated satisfies either or both of the following requirements (i) and (ii): A laminate that satisfies the following and has a dielectric constant difference of 0.15 or more between the layer (A) and the layer (B) .
(i) 10-point average roughness (Rz) is 0.3 μm or more (ii) Arithmetic average roughness (Ra) is 0.05 μm or more The laminate according to any one of claims 1 to 3 , wherein the maximum height roughness (Ry) of at least one surface of the layer (A) is 0.3 μm or more. The laminate according to any one of claims 1 to 4 , wherein the average interval (Sm) of the unevenness on the surface of at least one side of the layer (A) is 90 μm or less. The laminate according to any one of claims 1 to 5 , wherein the surface roughness of at least one side of the layer (B) satisfies either or both of the following requirements (iii) and (iv). .
(iii) 10-point average roughness (Rz) is 0.3 μm or more (iv) Arithmetic average roughness (Ra) is 0.05 μm or more The laminate according to any one of claims 1 to 6 , wherein the maximum height roughness (Ry) of at least one surface of the layer (B) is 0.4 μm or more. The laminate according to any one of claims 1 to 7 , wherein the average spacing (Sm) of the unevenness on the surface of at least one side of the layer (B) is 70 μm or less. The laminate according to any one of claims 1 to 8 , wherein the resin (a) is a polyester resin. The laminate according to any one of claims 1 to 9 , wherein the resin (b) is a silicone resin. The laminate according to any one of claims 1 to 10 , wherein the resin (a) is a polyethylene terephthalate resin. The laminate according to any one of claims 1 to 11 , which is used for press molding. A press molding method using the laminate according to any one of claims 1 to 12 , wherein a molded body is placed between the laminates so that the layer (B) side is the molded body side. A press molding method characterized by placing.