TWI581968B - Mold-release polyester film for mold process - Google Patents

Description

Mold release polyester film for molding process

The present invention relates to a release polyester film for a molding process. In particular, it is a release polyester film for a molding process which is excellent in mold conformability and slidability with a mold and conforms to workability.

In order to protect or shield an electronic component such as a semiconductor wafer from an external environment (external gas, contaminant, light, magnetic gas, high frequency, and the like), the electronic component such as a semiconductor resin is mounted on the substrate in a package sealed with a resin (molding resin). Typically, after heating a thermosetting resin (molding resin) such as a molten epoxy resin, an electronic component such as a semiconductor wafer is transferred to an installed mold, and is formed by transfer molding and curing. In the molding process, in order to prevent the molding resin from adhering to the mold, the molding resin is injected into the mold by the state of coating the resin molded portion (mold surface) of the mold with the release film, so that the molding resin does not directly contact the mold. The cavity is encapsulated. Such a release film for a molding process is proposed as a film of Patent Documents 1 to 3.

Prior technical literature

Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2002-361643

Patent Document 2 Japanese Patent Laid-Open Publication No. 2004-79566

Patent Document 3 Japanese Patent Laid-Open Publication No. 2001-250838

In recent years, along with the improvement in productivity, when the mold release film is pressed into the mold package, the problem of forming defects due to the air being eaten between the release film and the mold has become apparent. Further with electronic construction The capacity of the device is also increased, and the shape thereof is also diversified, and in the case where the relatively large electronic component is insufficient in compliance with the mold.

The object of the present invention is to solve the aforementioned problems. That is, a release polyester film for a molding process is provided, which is excellent in mold conformability and slidability with a mold, and conforms to workability.

The release polyester film for a molding process of the present invention which can solve the above problems is constituted as follows.

The first invention is a release polyester film for a molding process, which has a coating layer on one side of the polyester film, the coating layer having a binder resin and at least one kind of particles, and the average particle diameter d of the particles is 0.1. ~1.2 μm, the ratio (d/t) of the average particle diameter d of the particles to the thickness t of the coating layer is 1.5 or more and 100 or less.

According to a second aspect of the invention, there is provided the release polyester film of the molding process, wherein the coating layer contains 0.01 to 3% by mass of the particles, and the static friction coefficient of the coating layer side is 0.9 or less, the dynamic friction coefficient is 0.8 or less, and degassing The index is below 200 seconds.

The third invention is the above-mentioned release polyester film for a molding process, wherein the particle has a particle size distribution (d75/d25) of 1.1 to 1.5.

The fourth invention is the above-mentioned release polyester film for a molding process, wherein the polyester film is composed of a copolymerized polyester or a copolymerized polyester and a homopolyester.

The fifth invention is the above-mentioned release polyester film for a molding process, wherein the binder resin is a polyester resin or a polyurethane resin.

The sixth invention is the above-mentioned release-molding polyester film for a molding process, wherein the polyester resin is contained in a hydrophobic copolymerizable polyester resin A polyester-based graft copolymer obtained by grafting a polymerizable unsaturated monomer with an acid anhydride of one type of double bond.

The seventh invention is the above-mentioned release polyester film for a molding process, wherein the polyurethane resin is a polycarbonate-based polyurethane resin.

The eighth invention is the above-mentioned release polyester film for a molding process, which has a film thickness of 15 to 80 μm.

Since the release polyester film for a molding process of the present invention has a coating layer composed of the opposite mask specific particles in the release layer, it has excellent slidability with a mold and conforms to workability. Further, in an appropriate aspect of the present invention, since the polyester film is rich in flexibility, it is excellent in conformability to a mold. Therefore, the release polyester film for a molding process of the present invention is suitably used as a process release film for a resin molding process of an electronic component.

[Formation for implementing the invention]

(coating layer)

The coating layer of the release polyester film for a molding process of the present invention is characterized by comprising a binder resin and at least one specific particle. Thereby, even if it is pressed, the degassing with the mold can be obtained, and the moldability of the molding process is appropriate. Hereinafter, each configuration of the coating layer of the present invention will be described in detail.

(adhesive resin)

The coating layer contains a binder resin. As the binder resin, at least one of a polyester resin, a polyurethane resin, or a polyacrylate resin can be used.

The polyester resin used in the coating layer is suitably a polyester-based graft copolymer. The polyester-based graft copolymer can obtain a suitable film strength because it can form a highly self-crosslinking structure. Film strength of the coating layer on the polyester-based graft copolymer In other words, a polymerizable unsaturated monomer containing an acid anhydride having at least one double bond is graft-polymerized to a hydrophobic copolymerizable polyester resin. Hereinafter, a suitable polyester-based graft copolymer will be described.

"Grafting" introduces a branched polymer composed of a polymer different from the main chain into the main polymer backbone. In the present invention, a polymerizable unsaturated monomer containing an acid anhydride having at least one double bond is preferably used in a state in which a hydrophobic copolymerizable polyester resin is dissolved in an organic solvent by using a radical initiator. The reaction is carried out to carry out graft polymerization. The reaction product after completion of the grafting reaction, in addition to the desired graft copolymer of the hydrophobic copolymerizable polyester and the polymerizable unsaturated monomer, also contains a hydrophobic copolymerizable polyester which is not subjected to grafting. A resin, and a polymer of the above unsaturated monomer which is not grafted to the hydrophobic copolymerizable polyester. The polyester-based graft copolymer used in the present invention is not only the above-mentioned polyester-based graft copolymer but also the unreacted hydrophobic copolymerizable polyester and the ungrafted unsaturated monomer. A reaction mixture of a polymer or the like.

The acid value of the polyester-based graft copolymer obtained by graft-polymerizing a polymerizable unsaturated monomer to a hydrophobic copolymerizable polyester resin is preferably 600 eq/10 ⁶ g or more. More preferably 1200 eq/10 ⁶ g or more.

Further, in order to obtain a graft copolymer, the mass ratio of the hydrophobic copolymerizable polyester resin to the polymerizable unsaturated monomer is desirably in the range of polyester/polymerizable unsaturated monomer = 40/60 to 95/5, and more. The expected range is 55/45~93/7, and the most desirable range is 60/40~90/10. When the mass ratio of the hydrophobic copolymerizable polyester resin is less than 40% by mass, the glass transition point (Tig) of the obtained coating layer becomes high, and the dependency at the time of molding may be lowered. On the other hand, when the mass ratio of the hydrophobic copolymerizable polyester resin is larger than 95% by mass, adhesion tends to occur easily.

The graft copolymer is in the form of a solution or dispersion of an organic solvent or a solution or dispersion of an aqueous solvent. In particular, in the form of a dispersion of an aqueous solvent, that is, a water-dispersible resin, it is preferred in terms of work environment and coating properties. Such a water-dispersible resin is usually obtained by graft-polymerizing at least one type of hydrophilic polymerizable unsaturated monomer to the above-mentioned hydrophobic copolymerizable polyester resin in an organic solvent, followed by adding water and distilling off the organic solvent.

The glass transition point (Tig) of the graft copolymer is preferably 70 ° C or lower, more preferably 50 ° C or lower. When the glass transfer point (Tig) is 70 ° C or less, the film is excellent in conformational processing after decoration.

In the present invention, the hydrophobic copolymerizable polyester resin is water-insoluble which is not inherently dispersed or dissolved in the essence of water. The composition of the diacid component of the hydrophobic copolymerized polyester resin is preferably from 60 to 99.5 mol% of the aromatic diacid, and from 0 to 40 mol% of the aliphatic diacid and/or the alicyclic diacid. The diacid containing a polymerizable unsaturated double bond is 0.5 to 10 mol%. In the case where the aromatic diacid is less than 60 mol% or the aliphatic diacid and/or the alicyclic diacid exceeds 40 mol%, there is a case where the particles are detached.

Further, in the case where the diacid having a polymerizable unsaturated double bond is less than 0.5 mol%, the polymerizable unsaturated monomer is less likely to efficiently graft the hydrophobic copolymerizable polyester resin, and vice versa. In the case of more than 10 mol%, the viscosity of the grafting reaction system is increased, which is less preferable because the uniform reaction is hindered. More preferably, the aromatic diacid is 70 to 98 mol%, the aliphatic diacid and/or the alicyclic diacid is 0 to 30 mol%, and the diacid having a polymerizable unsaturated double bond is 2 to 7 mol. ear%.

Examples of the aromatic diacid include terephthalic acid, isophthalic acid, phthalic acid, naphthalened acid, and biphenyl diacid. a dihydric acid containing a hydrophilic group such as sodium 5-thioisophthalate, for the purpose of reducing the blocking resistance of the present invention Good for not using. Examples of the aliphatic diacid include succinic acid, adipic acid, sebacic acid, sebacic acid, dodecanedioic acid, and dimer acid, and the alicyclic diacid may, for example, be 1,4-cyclohexane. An acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, an acid anhydride thereof, and the like. Examples of the diacid having a polymerizable unsaturated double bond include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and unsaturated double bonds of α,β-unsaturated diacid. 2,5-nordecene dianhydride of alicyclic diacid, tetrahydrophthalic anhydride, and the like. Among them, in terms of polymerizability, fumaric acid, maleic acid, and 2,5-nordecene diacid are preferred.

On the other hand, the diol component may, for example, be an aliphatic diol having 2 to 10 carbon atoms and/or an alicyclic diol having 6 to 12 carbon atoms and/or a diol having an ether bond. Examples of the aliphatic diol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and neopentyl glycol. 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, and the like. Examples of the alicyclic diol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol and the like.

Examples of the diol having an ether bond include diethylene glycol, triethylene glycol, dipropylene glycol, and glycols obtained by adding ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols. For example, 2,2-bis(4-hydroxyethoxyphenyl)propane or the like. Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can also be used as needed.

In the hydrophobic copolymerizable polyester resin, 0 to 5 mol% of a trifunctional or higher polycarboxylic acid and/or a polyhydric alcohol may be copolymerized, and a trifunctional or higher polycarboxylic acid may be used as a 1,2,4-benzenetricarboxylic acid. (anhydride), 1,2,4,5-benzenetetracarboxylic acid (anhydride), diphenyl ketone tetracarboxylic acid (anhydride), 1,3,5-benzenetricarboxylic acid, ethylene glycol bis (1, 2, 4 - benzoic acid ester), glycerol ginseng (1,2,4-benzenetricarboxylate), and the like. On the other hand, as the trifunctional or higher polyhydric alcohol, glycerin, trimethylolethane, trimethylolpropane, neopentylol or the like is used. a trifunctional or higher polycarboxylic acid and/or a polyhydric alcohol, relative to All of the acid components or all of the diol components are copolymerized in a range of 0 to 5 mol%, and desirably in a range of 0 to 3 mol%, and if it exceeds 5 mol%, gelation tends to occur during polymerization. Not good. Further, the molecular weight of the hydrophobic copolymerizable polyester resin is preferably from 5,000 to 50,000 by weight average. When the molecular weight is less than 5,000, the particles may fall off. On the other hand, if it exceeds 50,000, problems such as gelation may occur during polymerization.

In the present invention, the polymerizable unsaturated single system grafted to the hydrophobic copolymerizable polyester resin is called a hydrophilic radical polymerizable monomer, and has a hydrophilic group, and has a group which can be changed to a hydrophilic group later. A monomer capable of free radical polymerization. Examples of the hydrophilic group include a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group, a decylamino group, and a quaternary ammonium salt group. On the other hand, examples of the group which can be changed to a hydrophilic group include an acid anhydride group, a glycidyl group, a chlorine group and the like. Among these bases, a carboxyl group is preferred in terms of enhancing the water dispersibility and the acid value of the graft copolymer. Therefore, it is desirable to contain at least one acid anhydride having a double bond as a polymerizable unsaturated monomer.

Examples of the polymerizable unsaturated monomer include fumaric acid monoester or diester of fumaric acid such as monoethyl fumarate, diethyl fumarate, and dibutyl fumarate; maleic acid and An acid anhydride; monoester or diester of maleic acid such as monoethyl maleate, diethyl maleate or dibutyl maleate; itaconic acid and its anhydride; monoester or diester of itaconic acid; Maleic acid such as phenyl maleate or the like; styrene derivatives such as styrene, α-methylstyrene, t-butylstyrene, and chloromethylstyrene; vinyltoluene, divinylbenzene, and the like. The acrylic polymerizable monomer which is one of the polymerizable unsaturated monomers may, for example, be an alkyl acrylate or an alkyl methacrylate (alkyl group is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, phenyl, benzyl, phenethyl, etc.): 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid 2- a hydroxyl group-containing acrylic monomer of hydroxypropyl ester or 2-hydroxypropyl methacrylate: acrylamide, methacrylamide, N-(methyl)methacrylamide, N-methyl acrylamide, N-(hydroxymethyl) acrylamide, N-(hydroxymethyl)methacrylamide, N,N-dimethylol decylamine, N-(methoxymethyl) decylamine, N -(Methoxymethyl)methacrylamide, N-phenylpropenylamine-containing acrylamide-containing acrylic monomer: N,N-diethylamine ethyl acrylate, N,N-N methacrylate Amino group-containing acrylic monomer containing diethylaminoethyl ester: glycidyl acrylate, glycidyl methacrylate, epoxy group-containing acrylic monomer: acrylic acid, methacrylic acid and their salts (sodium salt, An acrylic monomer containing a carboxyl group or a salt thereof, such as a potassium salt or an ammonium salt. The polymerizable unsaturated monomer may be copolymerized by using one type or two or more types, but it is desirable to contain at least one type of acid anhydride having a double bond. Among the above monomers, maleic anhydride is preferably used as the acid anhydride having a double bond. The other polymerizable unsaturated monomer combined with maleic anhydride is preferably styrene. Further, esters of such acid anhydrides may also be included.

As the graft polymerization initiator, organic peroxides and organic azo compounds which are well known to those skilled in the art can be used. Examples of the organic peroxide include benzamidine peroxide and tertiary butyl peroxyisobutyrate, and examples of the organic azo compound include 2,2'-azobisisobutyronitrile and 2,2'-azo double. (2,4-Dimethylvaleronitrile) and the like. The amount of the polymerization initiator used for the graft polymerization is at least 0.2% by mass, preferably 0.5% by mass or more based on the polymerizable unsaturated monomer. In addition to the polymerization initiator, a chain shifting agent for adjusting the chain length of the branched polymer, such as octyl mercaptan, hydrazine ethanol, 3-tributyl-4-hydroxyanisole or the like, may be used as needed. In this case, it is desirable to add the polymerizable unsaturated monomer in the range of 0 to 5% by mass.

In addition, as a copolymerization component of the copolymerized polyester, a diacid which includes a small amount of a guanamine bond, an amine ester bond, an ether bond, a carbonate bond or the like may be contained. Divided into diol components. Further, in order to increase the surface hardness of the obtained coating film, it is also possible to use 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1, 2, 4 in a ratio of 5 mol% or less. A monomer having a polycarboxy group such as 5-benzenetetracarboxylic acid, trimellitic anhydride, or 1,2,4,5-benzenetetracarboxylic anhydride is used as a copolymerization component of the above polyester. In the case where the monomer having a polycarboxy group exceeds 5 mol%, the obtained copolymerized polyester becomes unstable to heat and is less likely to be gelated.

The binder resin used in the coating layer of the present invention is preferably a polyurethane resin. The polyurethane can impart flexibility to the coating layer and exhibit excellent formability. The polyurethane resin is roughly classified into a polyester-based polyurethane resin, a polyether-based polyurethane resin, and a polycarbonate-based polyurethane resin. Among them, polycarbonate-based polyurethanes are preferably used in terms of blocking resistance and heat resistance. The polyester-based polyurethane resin is easily hydrolyzed in a hot and humid environment, and the polyether-based polyurethane resin is likely to have a film strength of the coating layer due to hygroscopicity. On the other hand, the polycarbonate-based urethane resin has a polycarbonate structure as a hard segment, and is suitably used because of its excellent heat resistance.

As the polycarbonate-based polyurethane resin, a polycarbonate diol, an aliphatic and/or alicyclic diisocyanate, and a polymer in which a chain extender is added as needed may be used. The constituents of these amine esters can be more determined by nuclear magnetic resonance analysis or the like.

The polycarbonate diol is represented by the following general formula.

HO-[-RO-COO-] _n -R-OH

(R is an aliphatic or alicyclic substituent)

The polycarbonate diol is one or more compounds selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate, and diols and/or polyether alcohols. It is obtained by a class reaction.

Examples of the alkyl carbonate are exemplified by ethyl acetate and 1,2-propane carbonate. Ester, 1,2-butylene carbonate, and the like.

Examples of the diaryl carbonate include diphenyl carbonate, phenyl naphthyl carbonate, dinaphthyl carbonate, 4-methyl diphenyl carbonate, 4-ethyl diphenyl carbonate, and 4-propyl diphenyl carbonate. Ester, 4,4'-dimethyldiphenyl carbonate, 4,4'-diethyldiphenyl carbonate, 4,4'-dipropyldiphenyl carbonate, and the like.

Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, and di-butyl butyl carbonate. Di-n-pentyl carbonate, diisoamyl carbonate, and the like.

As a co-reactant of such carbonates, first, examples of the diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, and 1,4- Butylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-methylpentanediol, 3-methylpentanediol, 2,2,4-trimethyl-1,6- Hexanediol, 2,3,5-trimethylpentanediol, and the like.

Further, examples of the polyether alcohols include, for example, polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, and epoxide adducts of diols. Examples of the diol used herein include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and isomers Alcohols, isomers of hexanediols or octanediols such as 2-ethyl-1,3-hexanediol, 1,2-bis(hydroxymethyl)cyclohexanone, 1,3-bis(hydroxyl) Methyl)cyclohexanone, 1,4-bis(hydroxymethyl)cyclohexanone, trimethylolpropane, glycerin, etc., and examples of the epoxide include ethylene oxide, propylene oxide, and 1 , 2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, phenylethylene oxide, epichlorohydrin, etc., may be used in combination of two or more kinds thereof. .

The above-mentioned diols and polyether alcohols may be used singly or in combination of two or more kinds thereof. Any of them is well known from the above alkyl carbonate, diaryl carbonate, dialkyl carbonate The polycarbonate diol can be formed by reacting one or more compounds selected from the group formed.

In the present invention, the composition molar ratio of the polyol of the constituent component of the amine ester is preferably from 3 to 100 mol%, more preferably 5, when the total polyisocyanate component of the amine ester is 100 mol%. ~50% by mole, further preferably 6-20% by mole. In particular, in the case of a polycarbonate polyol, if the compositional molar ratio is low, there is a case where the effect of moist heat resistance cannot be obtained. In the case where the aforementioned composition of the molar ratio is high, there is a case where the adhesion is lowered.

The polyisocyanate which is a constituent component of the amine ester of the present invention may, for example, be an isomer of toluene diisocyanate, an aromatic diisocyanate such as 4,4-diphenylmethane diisocyanate or an aromatic aliphatic group such as a diisocyanate. Diisocyanate, isophorone diisocyanate, alicyclic diisocyanate such as 4,4-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, hexamethylene diisocyanate And an aliphatic diisocyanate such as 2,2,4-trimethylhexamethylene diisocyanate or a polyisocyanate obtained by preliminarily adding a single compound or a plurality of such compounds to trimethylolpropane or the like.

Examples of the chain extender include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol, glycerin, and trimethylolpropane. And polyvalent alcohols such as pentaerythritol, diamines such as ethylenediamine, hexamethylenediamine, and piperazine, amine alcohols such as monoethanolamine and ethanolamine, and sulfur diethylene glycol such as sulfur diethylene glycol. Class, or water.

The coating layer of the present invention is preferably provided by an in-line coating method using an aqueous coating liquid. Therefore, the amine ester resin of the present invention is desirably water soluble. The above "water-soluble" means an aqueous solution which is dissolved in water or contains a water-soluble organic solvent of less than 50% by mass.

In order to impart water solubility to the amine ester resin, it can be introduced into the molecular skeleton of the amine ester. (copolymerization) a sulfonic acid (salt) group or a carboxylic acid (salt) group. The sulfonic acid (salt) group is strongly acidic, and it is difficult to maintain moisture resistance due to its hygroscopic property. Therefore, it is suitable to introduce a weakly acidic carboxylic acid (salt) group.

In order to introduce a carboxylic acid (salt) group into the amine ester resin, for example, as a polyol component, a polyol compound having a carboxylic acid group such as dimethylolpropionic acid or dimethylolbutanoic acid is introduced as a copolymer component. It is neutralized with a salt forming agent. Specific examples of the salt forming agent include trialkylamines such as ammonia water, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, and tri-n-butylamine, N-methylmorpholine, and N-ethylmorpholine. N-dialkylolamines such as N-alkylmorpholine, N-dimethylethanolamine, and N-diethylethanolamine. They may be used alone or in combination of two or more.

In order to impart water solubility, in the case where a polyol compound having a carboxylic acid (salt) group is used as a copolymer component, the composition of the polyol compound having a carboxylic acid (salt) group in the amine ester resin is When the total polyisocyanate component of the urethane resin is 100 mol%, it is preferably 3 to 60 mol%, more preferably 10 to 40 mol%. In the case where the aforementioned composition molar ratio is less than 3 mol%, there is a case where water dispersibility is difficult.

In the present invention, it is preferred to control the glass transition point (Tig) of the polyurethane resin to a specific range. That is, the glass transition point (Tig) of the polyurethane of the present invention has a lower limit of 40 ° C, preferably 50 ° C, and an upper limit of 100 ° C, preferably 90 ° C. When the glass transition point (Tig) of the polyurethane resin is less than 40 ° C, the blocking resistance may be lowered. Conversely, if it exceeds 100 ° C, the flexibility of the coating layer may be lowered. In order to control the glass transition point (Tig) of the polyurethane to the above range, it can be carried out by appropriately selecting and adjusting the molecular weight of the following polyol component or polyurethane.

In the present invention, in order to achieve a higher degree of flexibility and film strength of the coating layer The ratio of the copolymerized polyester to the aforementioned polyurethane is preferably a copolymerized polyester/polyurethane (mass ratio) = 80/20 to 30/70. The aforementioned blending ratio is preferably 75/25 to 40/60. If the copolymerized polyester/polyurethane (mass ratio) = 100/0 to 90/10, the flexibility of the coating layer may be lowered, and if it is 20/80 to 0/100, the blocking resistance may be lowered. situation.

The lower limit of the glass transition point (Tig) of the coating layer of the present invention is 30 ° C, preferably 35 ° C, and the upper limit is 55 ° C, preferably 50 ° C. If the glass transition point (Tig) of the coating layer is less than 35 ° C, there is a case where the blocking resistance is sufficiently lowered. When the glass transition point (Tig) of the coating layer exceeds 55 ° C, the flexibility of the coating layer is lowered. In order to appropriately consider both the film strength and the formability, it is preferred to set the glass transition point (Tig) of the coating layer to such a range. Even in the case of a glass transition point (Tig) in which the polyester component and the polyurethane component are within the above-mentioned ranges, in the case where a coating layer having a crosslinked structure is laminated in a film forming process together with a crosslinking agent, there is also a glass transition. The point (Tig) exceeds 55 °C. Even if there is a cross-linking structure, in order to maintain the glass transition point (Tig) in the above range, it is preferred to mix an appropriate amount of the crosslinking agent, the amount of the polyurethane compound, the amount of the polyester-based graft copolymer, and the hydrophobicity. The mass ratio of the polymerizable polyester resin to the polymerizable unsaturated monomer is within the above range. The above-mentioned glass transition point means a state in which a layer is laminated in a film forming process, that is, in a state in which a polyester-based graft copolymer and a polycarbonate-based polyurethane are crosslinked by a crosslinking agent, according to JIS-K7121 The extrapolated glass transition starting temperature (Tig) determined by the method.

(particle)

The coating layer of the present invention preferably contains at least particles having an average particle diameter of 0.1 to 1.2 μm.

If the surface of the film is smooth, the air that is drawn into the mold and the film during the molding process cannot be removed, and the air derived from the film is easily generated. The wrinkles of the department. In the case of using a film having such a drawback, it may become an appearance defect, and an appropriate component appearance cannot be obtained. Such an appearance disadvantage is that a thin film having a film thickness of, for example, 100 μm or less, particularly, for example, 80 μm or less may be liable to cause a low degree of softness of the film. Therefore, the coating layer of the present invention preferably contains particles having an average particle diameter of 0.1 to 1.2 μm. The average particle diameter of the particles is more preferably 0.2 to 1.0 μm, still more preferably 0.3 to 0.90 μm. When the lower limit of the average particle diameter is at least the above, effective projections can be formed on the surface of the coating layer, and by the improvement in deaeration property, a module having no appearance defects can be suitably obtained. When the average particle diameter of the particles is at most the above upper limit, the surface smoothness of the film can be obtained. The average particle diameter (number average particle diameter) of the particles can be measured by a scanning microscope observation of the surface of the film coating layer or an electron microscope observation of the film coating layer section, or by a Coulter counter. Among them, the particle diameter of the particles exposed on the surface of the coating layer can be measured by a scanning microscope observation on the surface of the film coating layer.

When the thickness of the coating layer is t (μm) and the average particle diameter of the particles is d (μm), the ratio (d/t) is 1.5 to 100, preferably 2 to 100, more preferably It is 3 to 50, further preferably 5 to 30, and particularly preferably 7 to 20. When (d/t) is at least the above lower limit, it is easy to form a surface protrusion which can be effectively degassed on the surface of the coating layer. On the other hand, when (d/t) is less than or equal to the above upper limit, dusting of particles (particles falling off from the coating layer) is less likely to occur, and a stable friction coefficient is easily obtained during processing.

The thickness of the coating layer of the present invention is specifically preferably 0.02 to 0.50 μm, more preferably 0.03 to 0.10 μm, still more preferably 0.04 to 0.08 μm.

The coating layer of the present invention has a good deaeration property because of the above configuration. Specifically, it is preferred that the degassing index measured by the method described later is 200. Less than seconds, more preferably less than 100 seconds, still more preferably less than 50 seconds. The outgassing index is below the above upper limit, and the degassing is good even if the film of the present invention is pressed into the mold at a specific pressure in the molding process. On the other hand, the lower limit of the outgassing index is preferably 30 seconds or longer, more preferably 35 seconds or longer. When the outgassing index is at least the above lower limit, dusting of the particle protrusions can be more appropriately suppressed.

The content of the particles in the coating layer is preferably from 0.01 to 3% by mass, more preferably from 0.05 to 2.5% by mass, still more preferably from 0.10 to 2.0% by mass. When the particle content is at least the above lower limit, good degassing properties can be maintained with the mold. On the other hand, when the particle content is equal to or lower than the above upper limit, dusting of the particle protrusions can be more appropriately suppressed.

The film concentration in the coating layer is in the above range, so that the film of the present invention has high transparency. Specifically, the film of the present invention preferably has a haze value of 2.0% or less, more preferably 1.5% or less, still more preferably 1.2% or less, particularly preferably 1.0% or less, and most preferably 0.8% or less. Further, in order to make the transparency of the film in the above range, it is preferred that the coating layer contains particles only, and the polyester film as the substrate has a structure substantially free of particles. The "substantially no particles are contained in the base film", for example, in the case of inorganic particles, the case where the inorganic element is quantified by X-ray fluorescence analysis, and the content is below the detection limit. In this case, even if particles are not intentionally added to the base film, a contaminated component derived from foreign matter or the like may be mixed.

In the case where the particle shape of the particles added to impart the deaeration property is not uniform, the fine unevenness on the surface of the film may be unevenly generated locally, and in the case where the multilayer film is laminated by the film roll, the unevenness of the uneven shape may occur. It accumulates, and there is a case where a fine surface of the film called orange peel is generated. The fine concavo-convex structure on the surface of the film thus formed is finer than the concavo-convex structure represented by a mat or the like, and has a surface roughness (SRa) or the like. The surface protrusion structure at the time of representation is a large structure. The uneven accumulation of the uneven shape of such particles is caused by a film having a thickness of, for example, 100 μm or less, particularly a film having a thickness of, for example, 80 μm or less, which tends to cause a low waist feeling of the film.

Therefore, the particle size distribution (d75/d25) of the aforementioned particles contained in the coating layer is preferably set to 1.1 to 1.5. The particle size distribution (d75/d25) of the particles is preferably 1.4 or less, more preferably 1.3 or less. When the particle size distribution of the particles is less than or equal to the above upper limit, uneven distribution of unevenness on the surface of the film is small, and even if the thin film is wound into a roll shape, orange streaks are less likely to occur. Further, the particle size distribution of the particles is preferably close to 1, and 1.1 is the lower limit in terms of industrial productivity. The means for controlling the particle size distribution of the particles in the above range is not particularly limited, and for example, filtration by a filter or the like, removal of coarse particles by a particle dropping speed, a blowing device, an electrostatic device, or the like, and selection of a particle species which are less likely to cause aggregation of particles, can be easily obtained. Small particle size distribution of organic particles, etc. The appropriate particle size distribution can be controlled by adjusting the concentration of the surfactant added when the particles are prepared by modulating the organic particles. In particular, the crosslinked organic particles obtained by emulsion polymerization are suitable because a narrow particle size distribution is easily obtained. The particle size distribution can be measured by a scanning microscope observation on the surface of the film coating layer or an electron microscope observation of the film coating layer slice, or can be obtained by Coulter counting method. Among them, the particle diameter of the particles exposed on the surface of the coating layer can be measured by a scanning microscope observation on the surface of the film coating layer.

Since the coating layer of the present invention has the above-described configuration, it is difficult to produce orange peel even when a thin film is wound up in a roll shape. The uneven structure of the surface of the film can be evaluated by a microwave scanner (manufactured by Gardner Co., Ltd.). The waveform scanner causes the laser point source to illuminate the laser beam at an angle of 60° to the perpendicular to the surface of the film, and the detector measures the opposite angle reflection of the perpendicular Light. The device detects the optical contour of the surface of the film by measuring the movement of the point source of the laser on the surface of the film to determine the interval between each point to determine the brightness of the reflected light. The detected optical profile analyzes the spectrum by frequency filtering and resolves the surface structure. The characteristic spectrum of this device is as follows. Du: wavelength 0.1mm or less, Wa: wavelength 0.1~0.3mm, Wb: wavelength 0.3~1mm, Wc: wavelength 1~3mm, Wd: wavelength 3~10mm, We: wavelength 10~30mm, SW: wavelength 0.3~1.2mm LW: The wavelength is 1.2~12mm. Among these, the reflection intensity (Wa) in the range of 0.1 to 0.3 mm in wavelength is applied as a contour due to a fine surface uneven structure.

In the case where the surface of the film of the present invention is measured by a waveform scanning device, the reflection intensity (Wa) in the range of 0.1 to 0.3 mm in wavelength is preferably 4.0 or less, more preferably 3.5 or less, still more preferably 3.0 or less. In the case where the aforementioned reflection intensity is below the above upper limit, the film surface may exhibit a smooth and appropriate appearance.

The foregoing particles contained in the coating layer of the present invention may, for example, be titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, vermiculite, alumina, talc, kaolin, clay, or the like, or a mixture thereof, and may be used in combination. Other general inorganic particles such as inorganic particles such as calcium phosphate, mica, lithium bentonite, zirconia, tungsten oxide, lithium fluoride, and calcium fluoride, and styrene-based, acrylate-based, melamine-based, benzoxazine-based, hydrazine-based Organic polymer particles such as oxygen. Among them, organic polymer-based particles such as styrene-based or acrylate-based particles in which particles having a narrow particle size distribution are easily obtained are preferably used.

In the present invention, it is preferred that at least one type of particle satisfies the above requirements. Further, it is also preferable to use a plurality of kinds of inorganic particles having different average particle diameters for the purpose of adding the above-mentioned particles to improve the blocking resistance and scratch resistance. The other particles used at this time are desirably smaller than the average particle diameter of the aforementioned particles. Further, it is more desirable to be smaller than the thickness of the coating layer. By adding such a relatively small other particle to impart hardness to the surface of the coating layer, the blocking resistance can be improved.

The particles having such a small average particle diameter (hereinafter referred to as particles B, and the particles are referred to as particles A to distinguish the two) preferably have an average particle diameter of 20 to 150 nm, more preferably 30 to 100 nm, and further More preferably 40 to 80 nm. When the average particle diameter of the particles B is dB and the thickness of the coating layer is t, the ratio (dB/t) thereof is preferably 1.5 to 0.1, more preferably 1.2 to 0.3. Since the particle B uses a small particle which is smaller than the particle A and has the same thickness as the coating layer, the film surface feeling is not impaired, and the blocking resistance can be improved. In the case where the particles B are added, the solid content concentration in the coating layer is preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less. By setting the addition concentration of the particles B to the above upper limit or less, the transparency of the film can be maintained. Further, the average particle diameter of the particles B can be appropriately determined by measuring the particle diameter of the particles exposed on the surface of the coating layer from the scanning microscopic observation pattern on the surface of the film coating layer as in the case of the above-mentioned particles A.

On the other hand, the coating layer of the present invention has good blocking resistance due to the above constitution. Specifically, the static friction coefficient of the coating layer measured by the method described later is preferably 0.9 or less, more preferably 0.8 or less, still more preferably 0.7 or less. The dynamic friction coefficient is preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.6 or less. The static friction coefficient and/or the dynamic friction coefficient are at most the above upper limit, and the film of the present invention has appropriate usability in various molding processes.

(crosslinking agent)

In terms of the point of blocking adhesion, the coating layer of the present invention preferably contains a crosslinking agent. Thereby, since the coating layer forms an appropriate crosslinked structure, it is possible to obtain more Proper film strength. The blending ratio of the crosslinking agent is preferably 5 to 40 parts by mass, and more preferably 8 to 25 parts by mass, per 100 parts by mass of the binder resin. When the blending ratio of the above-mentioned crosslinking agent is less than 5 parts by mass based on 100 parts by mass of the binder resin, it is less preferable because the blocking resistance is lowered. On the other hand, if it exceeds 40 parts by mass, the flexibility for depending on the mold may be lowered.

The crosslinking agent is a phenol formaldehyde resin which is a condensate of formaldehyde, such as an alkylated phenol or a cresol, and formaldehyde, and an adduct of formaldehyde, such as urea, melamine, benzoxazine, etc., and the adduct and the carbon number of 1 An amine-based resin such as an alkyl ether compound composed of an alcohol of -6; a polyfunctional epoxy compound; a polyfunctional isocyanate compound; a blocked isocyanate compound; a polyfunctional nitrogen aziridine compound; an oxazole compound.

The phenol formaldehyde resin may, for example, be an alkylated (methyl, ethyl, propyl, isopropyl or butyl) phenol, a tertiary pentyl phenol, a 4,4'-second butylene phenol, a tertiary butyl group. Phenol, o-, m-, p-cresol, p-cyclohexanol, 4,4'-isopropylidene phenol, p-nonyl phenol, p-octyl phenol, 3-pentyl phenol, phenol, benzene A condensate of phenols such as o-cresol, p-phenylphenol, and indophenol with formaldehyde.

The amine-based resin may, for example, be methoxymethylurea, methoxymethyl N, N-ethylene urea, methoxymethyl dicyandiamide, methoxymethyl melamine methoxide or hydroxymethyl benzoxazine methoxide. And butyloxymethyl melamine, butylated hydroxymethyl benzoxazine, etc., preferably methoxymethyl melamine methoxide, butyl oxymethyl melamine, and hydroxymethyl benzoxazine.

The polyfunctional epoxy compound may, for example, be a diglycidyl ether of bisphenol A or an oligomer thereof, a diepoxypropyl ether of hydrogenated bisphenol A, an oligomer thereof, and a bis(ethylene oxide) phthalate. Propyl ester, diglycidyl isophthalate, diglycidyl terephthalate, diglycidyl oxybenzoate, tetrahydrohydroquinone Glycidyl acrylate, diglycidyl hexahydrophthalate, diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, ethylene glycol diepoxypropyl Ether, propylene glycol diepoxypropyl ether, 1,4-butanediol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether and polyalkylene glycol diepoxypropyl ether , triglycidyl phthalate, triepoxypropyl isocyanate, 1,4-diepoxypropyl oxybenzene, diepoxypropyl propionaldehyde, glycerol triepoxypropyl ether, three Hydroxymethylpropane triepoxypropyl ether, neopentyl alcohol triepoxypropyl ether, glycerol adductoxide adduct, triepoxypropyl ether, and the like.

As the polyfunctional isocyanate compound, a low molecular or high molecular aromatic, an aliphatic diisocyanate or a trivalent or higher polyisocyanate can be used. Polyisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, diterpene diisocyanate, hydrogenated diisocyanate, isophorone a terpolymer of a diisocyanate and their isocyanate compounds. Further, an excessive amount of such an isocyanate compound and a low molecular weight active hydride such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine or triethanolamine may be mentioned. Or a terminal isocyanate group-containing compound obtained by reacting a polymer active hydride such as a polyester polyol, a polyether alcohol or a polyamine.

In the coating liquid for coating layer of the present invention, well-known additives such as an antioxidant, a heat stabilizer, a weathering stabilizer, an ultraviolet absorber, and an organic slip can be added to the extent that the effects of the present invention are not impaired. Agents, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents, and the like.

The method of providing the coating layer can be applied to a commonly used method such as gravure coating, kiss coat, immersion, spray coating, curtain coating, air knife coating, blade coating, reverse roll coating, and the like.

At the stage of applying the coating layer, in the method of coating before the film stretching, the method of coating after the longitudinal stretching, the method of applying the film to the surface of the film after the alignment treatment, etc., the crystallization of the polyester film of the substrate It is a preferred method to apply the coating before the completion of the alignment, and then to perform the on-line coating method of the crystal alignment of the polyester film after stretching in at least one direction, since the effect of the present invention can be more prominently exhibited.

(release layer)

The release layer has no adhesion to the molding resin, and depending on the deformation of the polyester film of the substrate, it is necessary to have a resin which does not cause wrinkles or cracking hardness, and is selected from water-soluble polyester, polyvinyl alcohol, A resin of an ethylene-vinyl alcohol copolymer resin, an ultraviolet curable acrylate resin, or an ultraviolet curable epoxy resin. Among them, the ultraviolet curable epoxy resin is suitable for adding a release layer at a low temperature. The thickness of the release layer is preferably in the range of 1 to 1000 nm, particularly preferably in the range of 10 to 500 nm. When the thickness of the mold release layer is at most the above lower limit, the mold release property with the molding resin may be deteriorated. When the thickness is at least the above upper limit, it is not possible to sufficiently follow the shape of the mold at the time of molding, and wrinkles may be generated on the surface of the module.

(substrate polyester film)

The polyester film to be a substrate is mainly formed of a polyester resin. The polyester resin constituting the base film is suitably polyethylene terephthalate, polyethylene naphthalate-2,6-ethylene diester, polytrimethylene terephthalate, polybutylene terephthalate, Or a copolymer containing a constituent component of the resin as a main component. Particularly in terms of mold compliance, a polyester film formed of a copolymerized polyester or a copolymerized polyester and a homopolyester is preferred.

As the release film for the molding process, the film thickness is preferably thin. The film thickness of the present invention is preferably 15 to 80 μm, more preferably 75 μm or less. The step is more preferably 60 μm or less, and particularly preferably 50 μm or less. Further, the film thickness is 15 μm or more, more preferably 20 μm or more, and still more preferably 25 μm or more in terms of film strength.

(copolymerized polyester)

The copolymerized polyester is suitably (a) a copolymerized polyester composed of an aromatic diacid component, and a diol component comprising ethylene glycol, and a branched aliphatic diol or an alicyclic diol, or (b) A copolymerized polyester composed of an aromatic diacid component containing terephthalic acid and isophthalic acid, and a diol component containing ethylene glycol. The polyester constituting the biaxially oriented polyester film is preferably a unit containing a 1,3-propanediol unit or a 1,4-butanediol of a diol component, and is preferable in terms of improving moldability. In the case of the above-mentioned (a), the copolymerized polyester used in the present invention preferably has a copolymerization component added such that the ratio of ethylene glycol to the total diol component is from 20 mol% to 95 mol. Further, the lower limit of the ratio of ethylene glycol to the total diol component is preferably 30 mol%, more preferably 40 mol%, and the upper limit is preferably 90 mol%, more preferably 80 mol%, further Good for 70%. Further, in the case of the above (b), the copolymerized polyester used in the present invention is preferably added in such a manner that the ratio of the terephthalic acid to the total aromatic diacid component is 50% by mole to 95% by mole. Polymeric ingredients. Further, the lower limit of the ratio of the terephthalic acid to the total aromatic diacid component is preferably 60 mol%, more preferably 70 mol%, and the upper limit is preferably 90 mol%.

The film raw material may be either a copolymer of a single copolymerized polyester, a mixture of one or more homopolyesters or a copolymerized polyester, or a combination of a homopolyester and a copolymerized polyester. Among these, the mixing method is suitable for suppressing the decrease in the melting point.

The copolymerized polyester is composed of an aromatic diacid component and a diol component containing ethylene glycol, a branched aliphatic diol or an alicyclic diol. In the case of a copolymerized polyester, the aromatic diacid component is suitable for terephthalic acid, isophthalic acid, naphthalic acid or an ester-forming derivative thereof, and terephthalic acid and/or relative to all diacid components. The amount of the naphthalenedicarboxylic acid component is 70 mol% or more, preferably 85 mol% or more, particularly preferably 95 mol% or more, and particularly preferably 100 mol%.

Further, examples of the branched aliphatic diol include neopentyl glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,4-butanediol. The alicyclic diol is exemplified by 1,4-cyclohexanedimethanol, tricyclodecane dimethanol or the like.

Among them, neopentyl glycol and 1,4-cyclohexane dimethanol are particularly preferred. Further, in the present invention, it is more preferable to add the above diol component and to use 1,3-propanediol and 1,4-butanediol as a copolymerization component. These diols are used as a copolymerization component, are suitable for imparting the above properties, and are excellent in transparency and heat resistance.

Further, in the case where the copolymerized polyester contains a copolymerized polyester comprising an aromatic diacid component of terephthalic acid and isophthalic acid and a glycol component containing ethylene glycol, ethylene glycol is used. The amount is 70 mol% or more, preferably 85 mol% or more, particularly preferably 95 mol% or more, and particularly preferably 100 mol%, based on the total diol component. The diol component other than ethylene glycol is suitably the above-mentioned branched aliphatic diol, alicyclic diol, and diethylene glycol.

As the catalyst used in the production of the above-mentioned copolymerized polyester, for example, an alkaline earth metal compound, a manganese compound, a cobalt compound, an aluminum compound, a cerium compound, a titanium compound, a titanium/cerium composite oxide, a cerium compound or the like can be used. Among these, as the point of catalyst activity, a titanium compound, a ruthenium compound, a ruthenium compound, or an aluminum compound is preferable.

In the production of the aforementioned copolymerized polyester, it is preferred to add a phosphorus compound as a thermal stabilizer. The phosphorus compound is preferably, for example, phosphoric acid, phosphorous acid or the like.

The intrinsic viscosity of the copolymerized polyester is preferably 0.50 dl/g or more, more preferably 0.55 dl/g or more, and particularly preferably 0.60 dl/g or more in terms of moldability and film stability. When the intrinsic viscosity is less than 0.50 dl/g, the formability tends to be lowered. On the other hand, in the case where a filter for removing foreign matter from the molten wire is provided, the upper limit of the intrinsic viscosity is preferably 1.0 dl/g at the point of discharge stability at the time of extruding the molten resin.

(Polyester resin as a film material)

In the present invention, the film raw material is one type or more of the homopolyester or the copolymerized polyester, and the film is formed by mixing them to maintain the same flexibility as in the case of using only the copolymerized polyester. On the one hand, transparency and high melting point (heat resistance) can be achieved. On the other hand, in the case of using a homopolymer polyester having a high melting point (for example, polyethylene terephthalate), on the one hand, high transparency is maintained, and on the other hand, flexibility and a melting point without practical problems can be achieved ( Heat resistance).

And mixing the copolymerized polyester and at least one of the homopolyesters other than polyethylene terephthalate (for example, polytetramethylene terephthalate or polybutylene terephthalate) The ester film is used as the raw material of the polyester film of the present invention, and it is further preferable in terms of formability.

In the present invention, a polyester resin alone or a polyester resin in which one or more kinds of homopolyesters or copolymerized polyesters are mixed is used as a film raw material. The polyester resin used in the present invention preferably contains a copolymerization component. Here, the copolymerization component is a case where (a) an aromatic diacid component and a diol component containing ethylene glycol, a branched aliphatic diol or an alicyclic diol constitute a copolymerized polyester. a component other than an aromatic diacid component and an ethylene glycol component, and (b) a copolymerization of an aromatic diacid component containing terephthalic acid and isophthalic acid, and a glycol component containing ethylene glycol In the case of polyester, it refers to benzoic acid. A component other than formic acid and ethylene glycol. The unit derived from such a copolymerization component preferably contains 5 to 50% by mass in the film.

The melting point of the polyester resin is preferably from 180 to 250 ° C from the viewpoint of heat resistance and moldability. The type and composition of the polymer to be used can be controlled in the range of the above-mentioned melting point to obtain a balance between formability and completion, and a high-quality molded article can be economically produced. Here, the melting point is the endothermic peak temperature at the time of melting detected by the so-called differential scanning calorimetry (DSC). This melting point was measured by a differential scanning card meter (DSC6200, manufactured by Seiko Instruments Co., Ltd.) at a temperature increase rate of 20 ° C/min. The lower limit of the melting point is more preferably 190 ° C, still more preferably 200 ° C, and particularly preferably 210 ° C or more. When the melting point is less than 180 ° C, the heat resistance tends to deteriorate. Therefore, there is a problem in that it is exposed to high temperatures during molding or when the molded article is used.

The upper limit of the melting point is preferably higher in terms of heat resistance. However, when the polyethylene terephthalate unit is the main component, the film having a melting point of more than 250 ° C tends to deteriorate in formability. And transparency also tends to deteriorate. Therefore, in order to obtain high moldability and transparency, the upper limit of the melting point is preferably controlled to 250 °C.

The polyester resin film of the present invention is preferably a biaxially stretched film. In the present invention, solvent resistance and dimensional stability of the unstretched sheet are improved by alignment of the biaxially stretched molecules. That is, it is possible to improve the solvent resistance and heat resistance of the defects of the unstretched sheet while maintaining the formability of a good unstretched sheet.

Further, in a preferred embodiment of the present invention, in order to obtain good transparency and stable workability (especially surface friction), a polyester layer having a film having a multilayer structure and containing only fine particles in the surface layer can be used. Such a substrate film It is preferably used in a surface layer (a layer) containing inert particles on both sides of a center layer (b layer), and a polyester film having a multilayer structure (a/b/a) which is laminated by a co-extrusion method. The layers constituting the surface layer in the watch may be of the same type or different types, and in order to maintain the planarity of the base film, it is desirable that the polyester resin of the surface layer in the surface has the same configuration.

(Production method)

The polyester film for forming of the present invention is desirably a biaxially oriented laminated polyester obtained by sequential biaxial stretching or simultaneous biaxial stretching. The following is a description of the best use of the sequential biaxial stretching method.

First, the raw material pellets are sufficiently dried under vacuum. Subsequently, the extruder was melted at a temperature higher than the melting point, and the polyester sheet was extruded in a layer form from a die by a co-extrusion method, and adhered to a rotary cooling roll to be solidified to obtain an unstretched polyester film. The method of attaching to the rotary cooling roll can be carried out by using a known electrostatic attaching method, an air knife method, a gas chamber method, or the like. It is also possible to blow air from the opposite side of the rotary chill roll as needed. The unstretched polyester film was guided to a roll type longitudinal stretching machine, and after heating at 80 to 125 ° C, the film was stretched 2.5 to 5.0 times in the longitudinal direction by the circumferential speed difference of the roll to obtain a uniaxially stretched film. Longitudinal stretching can be carried out in one stage or in multiple stages.

After that, the uniaxially stretched polyester film is guided to a clamp type transverse stretching machine, and after heating at 80 to 180 ° C, it is stretched 2.5 to 5.0 times in the transverse direction, and then heat-fixed at 200 to 240 ° C. If necessary, the film is tempered in the longitudinal direction and/or the transverse direction by 1 to 10%, and then wound up by a film winder to obtain a biaxially stretched polyester film.

(molding)

The release polyester film for molding process of the present invention can be used in resin molding of electronic components such as semiconductor wafers in the same manner as the conventional release polyester film. Process. That is, the electronic component such as the semiconductor wafer to be molded and the release polyester film of the present invention are placed at a specific position in the molding die in such a manner that the release layer is on the side of the electronic component, and the vacuum is attracted after the mold is closed. The release polyester film is adsorbed on the mold surface, and the molding resin may be transferred and formed between the mold release polyester film covering the electronic component and the mold surface. The molding method is not particularly limited, and it can be formed by vacuum molding, compression molding, mold molding, or the like.

Example

Embodiments and comparative examples of the present invention will be described below. First, the measurement/evaluation method used in the present invention will be described below.

(1) Glass transfer point (Tig)

The glass transition point (Tig) of the coating layer was measured by cutting off only the coating layer from the film.

The measurement was carried out in accordance with JIS K7121 using a differential scanning card meter (manufactured by Seiko Instruments Co., Ltd., DSC6200), and the glass transition start temperature (Tig) was obtained from the DSC curve.

Measuring condition

(a) Measurement temperature range: 0~200°C

(b) Heating rate: 20 ° C / min

(c) nitrogen flow

(2) Intrinsic viscosity

A 0.1 g shaving sample of the fine scale was dissolved in 25 ml of a mixed solvent of phenol/tetrachloroethane = 6/4 (mass ratio), and measured at 30 ° C using an Oswald viscometer. The measurement system was carried out 3 times, and the average value was obtained.

(3) Fog value

According to JIS-K7105, using an integrating sphere type transmittance measuring device (Japan Evaluation by Electrochromic Industrial Co., Ltd.).

(4) Coating layer thickness

The cross section of the film was cut at right angles to the film surface by a microtome, and a cross-sectional photograph of the film was taken by a transmission electron microscope (TEM), and the thickness of the resin component was measured on the photograph. The same measurement was performed 10 times in the place of change, and the average of the measured values was the thickness (μm) of the resin component.

(5) Measuring the appearance by waveform scanning

The obtained film of about 100 m length was wound into a film roll, and after standing at room temperature for about 12 hours, the film was cut, and a enamel sheet (GA board FS black 26) was attached to the opposite side of the coating layer, and a waveform scan was used. The device (manufactured by BYK Gardner Co., Ltd.) measures the coating level of the film. The value of the reflection intensity Wa in the range of 0.1-0.3 mm of the displayed wavelength was evaluated. The reflection intensity Wa in the range of 0.1 to 0.3 mm in wavelength is an index of the amplitude of the surface roughness, and the amplitude of the fine concavo-convex shape in accordance with the orange peel on the surface of the film can be evaluated. The smaller the value, the higher the smoothness of the surface.

(6) Particle size distribution of particle A

The particle size distribution value was measured by a S3500 scanning electron microscope (magnification: 800 times) manufactured by Hitachi, Ltd., and the particles exposed on the surface of the coating layer were measured by a photographic method and converted into equivalent balls. The particle size distribution measures the particle size of about 500 particles, and the calculated volume is accumulated from the small particle side. The particle diameter when the cumulative ratio was 25% with respect to the total volume was set to d25, the particle diameter when the cumulative ratio was 75% was set to d75, and the sharpness of the particle size distribution was shown by the ratio of (d75/d25). The closer this value is to 1, the sharper it is. On the other hand, in the case where the particles B coexist, the particle group having a large particle diameter is used as a parent group and measured by the above method.

(7) Average particle size of particles

The average particle diameter of the particles is determined by the same method as the above-described particle size distribution. Taken as a particle diameter d50 with respect to the total volume and the cumulative ratio of 50%. In the case where the particles B coexist, the particle group is divided into a large particle group and a parent group having a small particle diameter, and the particle diameter of the particle having a large particle diameter is particle A, and the particle diameter of the particle having a small particle size is particle B, and is measured by the above method. .

(8) Friction evaluation (μs‧μd)

A sample film having an area of 8 cm × 5 cm was cut out from the obtained film. This was fixed to the bottom surface of a 4.4 kg metal rectangular parallelepiped having a bottom surface having a size of 6 cm × 5 cm so that the coating layer was on the inner side. At this time, the 5 mm width direction of the sample film and the 5 cm width direction of the metal rectangular parallelepiped were aligned, and the longitudinal direction of the sample film was bent, and the tape was fixed to the side surface of the metal rectangular parallelepiped.

Next, a sample film having an area of 20 cm × 10 cm was cut out from the same film, and the coating layer was fixed to the flat metal plate with the tape in the longitudinal direction at the upper layer. The measurement surface is placed in contact with the measurement surface of the metal rectangular parallelepiped to which the sample film is attached, and the static friction coefficient (μs) and the dynamic friction coefficient (μd) are measured under the conditions of a tensile speed of 200 mm/min, 23 ° C, and 65% RH. . The measurement was performed using RTM-100 manufactured by Toyo BALDWIN Co., Ltd., and the static friction coefficient (μs) and the dynamic friction coefficient (μd) were calculated in accordance with JIS-K7125.

(9) Degassing index

As shown in Fig. 1, the film 4 is placed on the table 1 with the reverse coating layer facing up. Next, the film control 2 is placed on top of the film 4, and after fixing, the film 4 is fixed while applying tension. Next, the film 5 is applied to the film control 2 with the coating layer facing downward. Next, the film control 8 is placed on the film 5, and the film controls 8, 2 and the table 1 are further fixed using the screws 3. Next, the cavity 2a and the vacuum pump 6 provided in the film control 2 are connected through the fine holes 2c and the pipe 7 provided in the film control 2. Then, the vacuum pump 6 is driven, Tension is applied to the film 5 by the adsorption of the cavity 2a. At the same time, the overlapping faces of the film 4 and the film 5 are decompressed by the thin holes 2d provided in the circumferential direction of the film control 2, so that the film 4 and the film 5 are bonded to each other from the outer peripheral portion on the overlapping surface thereof. The manner of bonding can be easily seen by observing interference fringes from the upper portion of the self-overlapping surface. On the other hand, the interference fringe was generated from the outer peripheral portion of the overlapping surface of the film 4 and the film 5, and the interference fringe was expanded toward the front surface of the overlapping surface until the operation was stopped (seconds), and this time (second) was taken as the degassing index. Further, two sheets of the measurement system were alternately repeated five times, and the average value thereof was calculated as a degassing index. The smaller the value of the outgassing index, that is, the shorter the time (seconds), the better the curling characteristics of the film.

The curling property was evaluated on the basis of the following criteria.

◎: less than 50 seconds of degassing index

○: Degassing index of 50 seconds or more and 200 seconds or less

△: greater than the degassing index of 200 seconds, less than 350 seconds

×: Degassing index of 350 seconds or more

(10) Formability

The film was heated by contact with a heating plate heated to 100 to 140 ° C for 4 seconds, and then subjected to press molding at a mold temperature of 30 to 70 ° C for 5 seconds. The shape of the mold used was a cup shape, the opening diameter was 50 mm, the bottom portion was 40 mm in diameter, and the depth was 40 mm, and all corners had a curvature of 0.5 mm in diameter. The obtained molded article was evaluated on the basis of the following criteria.

○: The edges and corners are intact, and there are no wrinkles and appearance defects.

△: Wrinkles were observed in one part.

×: Wrinkles were observed on the entire surface, or damage was observed in the molded article.

(11) Sliding off of coating layer particles

Keep the direction of the mold that meets the coating layer constant, continuous The formation is based on (10) 200 times. The stain that was observed by the slippage of the particles on the surface of the mold was judged to be ×, the slightly observed one was judged as Δ, and the unobserved one was judged as ○.

Comparative example 1

(Preparation of hydrophobic polymerized polyester resin)

Injecting 218 parts by mass of dimethyl terephthalate, 194 parts by mass of dimethyl isophthalate, 488 parts by mass of ethylene glycol, 200 mass in a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux cooler The neopentyl glycol and 0.5 parts by mass of tetra-n-butyl titanium were subjected to a transesterification reaction at 160 ° C to 220 ° C for 4 hours. Next, 13 parts by mass of fumaric acid and 51 parts by mass of sebacic acid were added, and the mixture was heated from 200 ° C to 220 ° C for 1 hour to carry out an esterification reaction. Subsequently, the temperature was raised to 255 ° C, and the reaction system was gradually depressurized, and then reacted under reduced pressure of 0.22 mmHg for 1 hour and 30 minutes to obtain a hydrophobic copolymerizable polyester resin. The obtained hydrophobic copolymerized polyester was light yellow transparent.

(Preparation of water-dispersed polyester-based graft copolymer)

To the reactor equipped with a stirrer, a thermometer, a reflux device, and a quantitative titration device, 75 parts by mass of a hydrophobic copolymerized polyester, 56 parts by mass of methyl ethyl ketone, and 19 parts by mass of isopropyl alcohol were added, and the mixture was heated to 65 ° C, and stirred to dissolve the resin. After the resin was completely dissolved, 15 parts by mass of maleic anhydride was added to the polyester solution. Next, 10 parts by mass of styrene and 1.5 parts by mass of azobisdimethyl valeronitrile were dissolved in 12 parts by mass of methyl ethyl ketone, and the mixture was dropwise added to the polyester solution at 0.1 ml/min., and stirring was further continued for 2 hours. After the sample was analyzed from the reaction solution, 5 parts by mass of methanol was added. Next, 300 parts by mass of deionized water and 15 parts by mass of triethylamine were added to the reaction solution, and the mixture was stirred for one and a half hours. Thereafter, the internal temperature of the reactor was raised to 100 ° C, and methyl ethyl ketone, isopropyl alcohol, and excess triethylamine were distilled off by distillation to obtain a water-dispersed polyester graft. Copolymer. The obtained polyester-based graft copolymer was light yellow and transparent, and the glass transition point was 40 °C. This resin was used as a polyester-based graft copolymer (a1).

(Synthesis of polycarbonate urethane resin)

Into a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer, 73.0 parts by mass of 1,3-cyclohexane bis(methyl isocyanate) as a polyisocyanate, and 112.7 parts by mass of a number average molecular weight were injected. 2000 polyhexadediol carbonate, 11.7 parts by mass of neopentyl glycol, 12.6 parts by mass of dimethanol propionic acid, 60 parts by mass of acetonitrile as an organic solvent, and 30 parts by mass of N-methylpyrrolidone in a nitrogen atmosphere Next, the temperature of the reaction liquid was adjusted to 75 to 78 ° C, and 0.06 parts by mass of stannous octoate as a reaction catalyst was added, and the reaction was carried out for 7 hours until the reaction rate was 99% or more. It was then cooled to 30 ° C to obtain an isocyanate group-terminated prepolymer. Next, 450 g of water was added to a reaction vessel equipped with a Homo Disper capable of high-speed stirring, and the mixture was adjusted at 25 ° C, stirred and mixed at 2000 min ^-1 , and water-dispersed while adding an isocyanate-based terminal prepolymer. Thereafter, a part of acetonitrile and water were removed under reduced pressure to prepare an aqueous dispersion (b1) of a water-dispersible polycarbonate-based urethane resin having a solid content of 35%. The glass transfer point (Tig) was 86 °C.

(Preparation of coating liquid A)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 5%, and 20 parts by mass of a block isocyanate compound (Takenate (registered trademark) WB-920, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.; the same applies hereinafter) is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin. And a polymethyl methacrylate particle having an average particle diameter of 0.04 μm as a particle of 1.0% by mass based on the total resin solid content of the resin, and a total particle diameter of 0.04 μm. The system, EPOSTAR (registered trademark) MX020W) is diluted with water/isopropanol mixed solvent (=65/35; mass ratio) to prepare a water-based coating agent.

(manufacturing film raw materials)

The dry components are respectively 100% by mole of terephthalic acid unit as an aromatic diacid component, 40% by mole of ethylene glycol unit as a glycol component, and 60% by mole of neopentyl glycol unit. The copolymerized polyester chip (A) of 0.69 dl/g and the polyethylene terephthalate chip (B) having an intrinsic viscosity of 0.69 dl/g. Further, the chip (A) and the chip (B) were mixed to have a mass ratio of 25:75.

(manufacturing film)

Next, these chipping mixtures were melt extruded at 270 ° C in a slit from a T die, and rapidly solidified on a cooling roll having a surface temperature of 40 ° C while being attached to the cooling by an electrostatic application method. Roll and obtain an amorphous unstretched sheet.

The obtained unstretched sheet was stretched 3.3 times between 90° C. in the longitudinal direction between the heating roll and the cooling roll.

Next, the obtained aqueous coating liquid A shown above was applied to one surface of the film by a roll coating method on a uniaxially stretched film, and dried at 130 ° C for 3 seconds to remove water.

Thereafter, the end portion was continuously guided by the clip to the tenter, heated at a setting of 100 ° C and laterally stretched by 3.8, and the heat-fixed side was applied at 230 ° C for 5 seconds, further by 205. The film was relaxed by 5% in the width direction at ° C to obtain a polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm.

Then, an ultraviolet cation-curable oxime resin (manufactured by Toshiba Silicone Co., Ltd., UV9315) was dispersed in a solvent (n-hexane) to have a resin solid content concentration of 2% by mass, and 1 part by mass of 100 parts by mass of the oxirane resin was used for hardening. A bis(alkylbenzene) hexafluoroantimonate iodine of a catalyst is used to prepare a coating liquid containing a cerium oxide resin. On the reverse coating layer of the polyester film, a coating liquid containing the above-described oxime resin is applied to one surface of the film by a wire roll, dried at 100 ° C for 30 seconds, and then irradiated with ultraviolet rays (300 mJ/cm ² ) by an ultraviolet irradiation device. A release polyester film (thickness of the release layer after drying of 100 nm) was produced.

The evaluation results of the obtained release polyester film are shown in Table 1.

(Preparation of coating liquid B)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass, and relative to the entire resin A method comprising 1.0% by mass of a vermiculite particle (manufactured by Nissan Chemical Industries, Ltd., SNOWTEX (registered trademark) XL) having an average particle diameter of 0.06 μm as a particle, and a mixed solvent of water/isopropyl alcohol (=65/35; The mass ratio is diluted to be used as a water coating agent.

Comparative example 2

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid B. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid C)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/ The polyurethane resin (mass ratio) was 95/5, and 20 parts by mass of the blocked isocyanate compound was mixed with respect to 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total solid content of the resin was 2.8. % by mass, and all of the resin, the total resin solid content concentration of 2.8% by mass and the average particle diameter of 0.13 μm of vermiculite particles (manufactured by Nissan Chemical Industries, Ltd., SNOWTEX (registered trademark) ZL), and relative to all resins The water-based coating agent was diluted with a mixed solvent of water/isopropanol (=65/35; mass ratio) so as to contain 7.3 mass% of vermiculite particles having an average particle diameter of 0.06 μm.

Example 1

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid C. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid D)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass, and relative to the entire resin A styrene/divinylbenzene crosslinked particle (manufactured by JSR Corporation, SX8743-08) having an average particle diameter of 0.83 μm of 0.02% by mass, and 7.3 mass% of vermiculite particles having an average particle diameter of 0.06 μm based on the entire resin. The method was diluted with a water/isopropyl alcohol mixed solvent (=65/35; mass ratio) to prepare a water-based coating agent.

Example 2

Except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid D, In the same manner as in Comparative Example 1, a release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid E)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass, and relative to the entire resin The styrene/divinylbenzene crosslinked particles having an overall resin solid content concentration of 0.05% by mass and an average particle diameter of 0.83 μm, and a method of containing 7.3% by mass of vermiculite particles having an average particle diameter of 0.06 μm with respect to the entire resin. It was diluted with water/isopropyl alcohol mixed solvent (=65/35; mass ratio) to prepare a water-based coating agent.

Example 3

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid E. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid F)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 0.56% by mass, and relative to the entire resin In terms of the total solid content of the resin, 1.0% by mass And a styrene/divinylbenzene crosslinked particle having an average particle diameter of 0.83 μm, and a mixed solvent of water/isopropanol in a manner of containing 7.3% by mass of vermiculite particles having an average particle diameter of 0.06 μm. 65/35; mass ratio) is diluted to be a water-based coating agent.

Example 4

A release polyester film having a coating thickness of 0.01 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid F. The properties of the obtained film and the evaluation results are shown in Table 1.

Using the release polyester film obtained in Example 4 as a molding process release film, resin bare semiconductor resin molding was performed. The semiconductor wafer substrate having a length of 150 mm, a width of 100 mm, and a height of 10 mm was set under the transfer molding in a 175 ° C environment, and the coating layer of the release polyester film obtained in Example 4 was vacuum-adsorbed as a mold surface. After the mold is closed, the upper and lower molds are closed, and the epoxy resin for semiconductor molding is used for transfer molding. The forming time was set to 90 seconds. The obtained semiconductor package has a good angularity and no problem in appearance.

(Preparation of coating liquid G)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 1.12% by mass, and relative to the entire resin A styrene/divinylbenzene crosslinked particle having 1.0% by mass of an average particle diameter of 0.83 μm, and a method of containing 7.3% by mass of vermiculite particles having an average particle diameter of 0.06 μm with respect to the entire resin, and water/isopropyl alcohol Mixed The solvent (=65/35; mass ratio) was diluted to prepare a water-based coating agent.

Example 5

A release polyester film having a coating thickness of 0.02 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid G. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid H)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass, and relative to the entire resin The styrene/divinylbenzene crosslinked particles having a total resin solid content concentration of 2.8% by mass and an average particle diameter of 0.83 μm, and a method of containing 7.3% by mass of vermiculite particles having an average particle diameter of 0.06 μm with respect to the entire resin. It was diluted with water/isopropyl alcohol mixed solvent (=65/35; mass ratio) to prepare a water-based coating agent.

Example 6

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid H. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid I)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and relative to polyester-based graft copolymers 100 parts by mass of the total amount of the polyurethane resin, 20 parts by mass of the blocked isocyanate compound are mixed, and the styrene/divinylbenzene crosslinked with an all resin solid content concentration of 5.04% by mass and an average particle diameter of 0.83 μm is obtained for all the resins. The particles are mixed with a solvent of water/isopropanol (=65/35; mass ratio) with respect to all the resins and a total of 7.3% by mass of vermiculite particles having an average particle diameter of 0.06 μm. Dilute it as a water coating agent.

Example 7

A release polyester film having a coating thickness of the coating layer of 0.09 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid I. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation coating solution J)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 5.60% by mass, and relative to the entire resin A styrene/divinylbenzene crosslinked particle containing 1.0% by mass of an average particle diameter of 0.83 μm, and a method of containing 7.3% by mass of vermiculite particles having an average particle diameter of 0.06 μm with respect to the entire resin, with water/isopropanol The mixed solvent (=65/35; mass ratio) was diluted to prepare a water-based coating agent.

Example 8

A release polyester film having a coating thickness of 0.10 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid J. Film properties obtained The evaluation results are shown in Table 1.

(Preparation of coating liquid K)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass, and relative to the entire resin A styrene/divinylbenzene crosslinked particle having 3.0% by mass of an average particle diameter of 0.83 μm, and a method of containing 7.3% by mass of vermiculite particles having an average particle diameter of 0.06 μm with respect to the entire resin, and water/isopropanol The mixed solvent (=65/35; mass ratio) was diluted to prepare a water-based coating agent.

Example 9

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid K. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid L)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass, and relative to the entire resin A styrene/divinylbenzene crosslinked particle having 5.0% by mass of an average particle diameter of 0.83 μm, and a method of containing 7.3% by mass of vermiculite particles having an average particle diameter of 0.06 μm with respect to the entire resin, and water/isopropyl alcohol. The mixed solvent (=65/35; mass ratio) was diluted to prepare a water-based coating agent.

Example 10

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid K. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid M)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass, and relative to the entire resin A styrene/divinylbenzene crosslinked particle (manufactured by JSR Corporation, SX8743-05) having 1.0% by mass of an average particle diameter of 0.47 μm, and 7.3 mass% of vermiculite particles having an average particle diameter of 0.06 μm based on the entire resin. The method was diluted with a water/isopropyl alcohol mixed solvent (=65/35; mass ratio) to prepare a water-based coating agent.

Example 11

Except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid M, in the same manner as in Comparative Example 1, a release polyester having a coating thickness of 0.05 μm at a film thickness of 25 μm after film formation was obtained. film. The properties of the obtained film and the evaluation results are shown in Table 1.

Example 12

Except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid M, in the same manner as in Comparative Example 1, a release polyester having a coating thickness of 0.05 μm at a film thickness of 75 μm after film formation was obtained. film. The properties of the obtained film and the evaluation results are shown in Table 1.

Example 13

In the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid M, a release polyester having a coating thickness of 0.05 μm at a film thickness of 20 μm after film formation was obtained. film. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid N)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass and the average particle diameter is 1.12 μm. The vermiculite particles (manufactured by Nippon Shokubai Co., Ltd., Seahostar (registered trademark) KE-P100) contained 1.7% by mass based on the total resin, and the vermiculite particles having an average particle diameter of 0.06 μm contained 7.3% by mass based on the total resin. The method was diluted with a water/isopropyl alcohol mixed solvent (=65/35; mass ratio) to prepare a water-based coating agent.

Example 14

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid N. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid O)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin. The benzoate/formaldehyde crosslinked particles (manufactured by Nippon Shokubai Co., Ltd., EPOSTAR) having a total resin solid content of 2.8% by mass and 1.0% by mass of an average particle diameter of 1.86 μm based on the entire resin system. (registered trademark) MS), and mixed with a resin containing 7.3% by mass of an average particle diameter of 0.06 μm, mixed with water/isopropyl alcohol mixed solvent (=65/35; mass ratio), As a water coating agent.

Comparative example 3

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid O. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid P)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass and the average particle diameter is 0.9 μm. The melamine/formaldehyde crosslinked particles (manufactured by Nippon Shokubai Co., Ltd., EPOSTAR (registered trademark) S6) are 1.0% by mass based on the total resin, and the vermiculite particles having an average particle diameter of 0.06 μm are 7.3% by mass based on the entire resin. The method was diluted with water/isopropyl alcohol mixed solvent (=65/35; mass ratio) to prepare a water-based coating agent.

Example 15

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid P. Film properties obtained The evaluation results are shown in Table 1.

(Preparation coating solution Q)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass and the average particle diameter is 1.58 μm. The meteorite particles (manufactured by Nippon Shokubai Co., Ltd., Seahostar (registered trademark) KE-P150) are 1.0% by mass based on the total resin, and the vermiculite particles having an average particle diameter of 0.06 μm are 7.3% by mass based on the total resin. The method was diluted with a water/isopropyl alcohol mixed solvent (=65/35; mass ratio) to prepare a water-based coating agent.

Comparative example 4

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid Q. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid R)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 80 /20, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass and the average particle diameter is 0.83 μm. The styrene/divinylbenzene crosslinked particles are 1.0% by mass based on the total resin, and the vermiculite particles having an average particle diameter of 0.06 μm are contained in an amount of 7.3% by mass based on the total resin, and are mixed with water/isopropyl alcohol. The solvent (=65/35; mass ratio) was diluted to prepare a water-based coating agent.

Example 16

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid R. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid S)

The solid content ratio of the copolymerized polyester resin liquid (a1) and the water-dispersible polycarbonate type amine ester resin (b1) obtained in the above is a copolymerized polyester resin/polyurethane resin (mass ratio) = 40/60, And 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the copolymerized polyester resin and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle diameter is 0.83 μm. The vinyl benzene crosslinked particles were 1.0% by mass based on the total resin, and the vermiculite particles having an average particle diameter of 0.06 μm were contained in an amount of 7.3% by mass based on the total resin, and a mixed solvent of water/isopropyl alcohol (=65/). 35; mass ratio) is diluted to be an aqueous coating agent.

Example 17

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid S. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid T)

The solid content ratio of the copolymerized polyester resin liquid (a1) and the water-dispersible polycarbonate type amine ester resin (b1) obtained in the above is a copolymerized polyester resin/polyurethane resin (mass ratio) = 80/20, And mixing 40 parts by mass of the block isocyanic acid with respect to 100 parts by mass of the total amount of the copolymerized polyester resin and the polyurethane resin The styrene/divinylbenzene crosslinked particles having a total resin solid content concentration of 2.8% by mass and an average particle diameter of 0.83 μm are 1.0% by mass based on the entire resin, and an average particle diameter of 0.06 μm is obtained. The particles were diluted with water/isopropyl alcohol in a mixed solvent (=65/35; mass ratio) so as to be 7.3% by mass based on the total resin, and used as an aqueous coating agent.

Example 18

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid T. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid U)

The solid content ratio of the copolymerized polyester resin liquid (a1) and the water-dispersible polycarbonate type amine ester resin (b1) obtained in the above is a copolymerized polyester resin/polyurethane resin (mass ratio) = 80/20, And 8 parts by mass of the block isocyanate compound is mixed with respect to 100 parts by mass of the total amount of the copolymerized polyester resin and the polyurethane resin, and the total resin solid content concentration is 2.8% by mass and the average particle diameter is 0.83 μm. The vinyl benzene crosslinked particles were 1.0% by mass based on the total resin, and the vermiculite particles having an average particle diameter of 0.06 μm were contained in an amount of 7.3% by mass based on the total resin, and a mixed solvent of water/isopropyl alcohol (=65/). 35; mass ratio) is diluted to be an aqueous coating agent.

Example 19

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid U. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid V)

The ratio of the copolymerized polyester resin liquid (a1) obtained in the above-mentioned, and the polyurethane resin (made by Mitsui Chemical Co., Ltd.: Takelac (registered trademark) W511) having a glass transition point of 35 ° C (catalog value) is a copolymerized polyester resin / The polyurethane resin (mass ratio) was 80/20, and 20 parts by mass of the blocked isocyanate compound was mixed with respect to 100 parts by mass of the total amount of the copolymerized polyester resin and the polyurethane resin, so that the total resin solid content concentration was 2.8% by mass. And the styrene/divinylbenzene crosslinked particle having an average particle diameter of 0.83 μm is 1.0% by mass based on the total resin, and the vermiculite particles having an average particle diameter of 0.06 μm are contained in an amount of 7.3% by mass based on the total resin. The mixed solvent of isopropyl alcohol (=65/35; mass ratio) was diluted to prepare a water-based coating agent.

Example 20

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid V. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating liquid W)

The solid content ratio of the polyester-based graft copolymer (a1) obtained in the above-mentioned manner and the ether-based polyurethane resin (Takelac (registered trademark) W6020 manufactured by Mitsui Chemicals Co., Ltd.) having a glass transition point of 90 ° C (catalog value) is agglomerated. The ester-based graft copolymer/polyurethane resin (mass ratio) is 80/20, and 20 parts by mass of the blocked isocyanate compound is mixed with 100 parts by mass of the total of the polyester-based graft copolymer and the polyurethane resin, so that The styrene/divinylbenzene crosslinked particles having a resin solid content concentration of 2.8% by mass and an average particle diameter of 0.83 μm were 1.0% by mass based on the total resin, and the vermiculite particles having an average particle diameter of 0.06 μm were made to the entire resin. For the method of containing 7.3% by mass, it is diluted with water/isopropyl alcohol mixed solvent (=65/35; mass ratio) to prepare for water coating. Cloth.

Example 21

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid W. The properties of the obtained film and the evaluation results are shown in Table 1.

Example 22

In the case of using a coating liquid H in place of the block isocyanate compound, a coating liquid having a melamine compound (BECKAMINE (registered trademark) M-3; solid content concentration: 60%) having a solid content of 16.7% by mass is used. A release polyester film having a coating thickness of 0.05 nm was obtained in the same manner as in Example 8 except for (X). The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation of coating solution Y)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass and the average particle diameter is 0.42 μm. The meteorite particles (MP4540-M, manufactured by Nissan Chemical Industries, Ltd.) are diluted with water/isopropyl alcohol (=65/35; mass ratio) to 1.0% by mass of the total resin. It is a water coating agent.

Example 23

In the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid Y, a coating layer was obtained at a film thickness of 25 μm. A release polyester film having a thickness of 0.05 μm was applied. The properties of the obtained film and the evaluation results are shown in Table 1.

(Preparation coating solution Z)

The solid content ratio of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based amine ester resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 95 /5, and 20 parts by mass of the block isocyanate compound is mixed with 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that the total resin solid content concentration is 2.8% by mass and the average particle diameter is 0.62 μm. The meteorite particles (Seahostar (registered trademark) KE-P50, manufactured by Nippon Shokubai Co., Ltd.) are 1.0% by mass based on the total resin, and mixed with water/isopropyl alcohol (=65/35; mass ratio). Dilute it as a water coating agent.

Example 24

A release polyester film having a coating thickness of 0.05 μm at a film thickness of 25 μm was obtained in the same manner as in Comparative Example 1, except that the coating liquid A in Comparative Example 1 was replaced with the coating liquid Z. The properties of the obtained film and the evaluation results are shown in Table 1.

[Industry Utilization]

The release polyester film of the molding process of the present invention is excellent in mold dependency and slidability with a mold. Therefore, the release polyester film for a molding process of the present invention is suitable for a release film in a resin molding process of an electronic component.

1‧‧‧Table

2, 8‧‧‧ film control

2a‧‧‧Ditch hole

2c‧‧‧ hole

2d‧‧‧Pore

3‧‧‧ screws

4, 5‧‧‧ film

6‧‧‧Vacuum pump

7‧‧‧pipe

X‧‧‧Film overlap

Fig. 1 is an explanatory view showing a cross section of a device for measuring the degassing rate of a film.

1‧‧‧Table

2, 8‧‧‧ film control

2a‧‧‧Ditch hole

2c‧‧‧ hole

2d‧‧‧Pore

3‧‧‧ screws

4, 5‧‧‧ film

6‧‧‧Vacuum pump

7‧‧‧pipe

X‧‧‧Film overlap

Claims (8)

A release polyester film for molding process, which has a coating layer on one side of the polyester film and a release layer on the other side; the coating layer has a binder resin and at least one content of 0.01 to 3% by mass The particles; the average particle diameter d of the particles is 0.1 to 1.2 μm; the thickness t of the coating layer is 0.02 to 0.50 μm; and the ratio (d/t) of the average particle diameter d of the particles to the thickness t of the coating layer is 1.5. Above 100 or less. The release polyester film for a molding process according to the first aspect of the invention, wherein the coating layer side has a static friction coefficient of 0.9 or less, a dynamic friction coefficient of 0.8 or less, and a degassing index of 200 seconds or less. The release polyester film for a molding process according to claim 1 or 2, wherein the particle has a particle size distribution (d75/d25) of 1.1 to 1.5. The release polyester film for a molding process according to claim 1 or 2, wherein the polyester film is composed of a copolymerized polyester or a copolymerized polyester and a homopolyester. The release polyester film for a molding process according to claim 1, wherein the binder resin is a polyester resin or a polyurethane resin. The release polyester film for a molding process according to claim 5, wherein the polyester resin is polymerized by an acid anhydride having at least one double bond in the hydrophobic copolymerizable polyester resin. A polyester-based graft copolymer obtained by grafting a saturated monomer. A release polyester film for a molding process according to claim 5 or 6, wherein the polyurethane resin is a polycarbonate-based polyurethane resin. For example, the release molding polyester film for the molding process of claim 1 or 2 The film has a film thickness of 15 to 80 μm.