TW202100590A - Block copolymer, release agent composition, release layer, and release sheet - Google Patents

Abstract

A block copolymer (A) having a first segment and a second segment, wherein the first segment is a polymer segment formed by a monomer component comprising a specific hydroxyl group-containing monomer and a specific polycyclic aliphatic hydrocarbon group-containing monomer, the second segment is a polymer segment formed by a monomer component comprising a specific long-chain alkyl group-containing monomer, and the content ratios of the monomers are specified amounts in all of the monomer components that form the block copolymer (A). The block copolymer enables the preparation of a release agent composition having a satisfactory usable time even when a crosslinking agent is used, and therefore enables the production of a release sheet having excellent releasability and hardness.

Description

Block copolymer, release agent composition, release layer and release sheet

The invention relates to a block copolymer, a release agent composition, a release layer and a release sheet.

The release sheet refers to a material such as a plastic film having a release layer on the surface of a base material, and is used, for example, for forming a support for materials such as synthetic leather or green sheets of electronic materials, and for protecting adhesive layers.

As a constituent of the release layer, for example, as disclosed in Patent Documents 1 and 2, compounds having a siloxane skeleton are widely used because of their excellent release properties.

On the other hand, in the release sheet used in the manufacturing process of electronic components such as laminated ceramic capacitors and semiconductor elements, silicon components derived from compounds having a siloxane skeleton may be transferred to the electronic components, thereby causing poor conductivity. Because of this, there is a need for a release sheet that does not contain silicon.

In Patent Document 3, as one of the release components containing no silicon component, a copolymer having a long-chain alkyl group is listed, and a release layer having a long-chain alkyl group-containing polymer is disclosed. Mold film (release sheet).

In addition, Patent Document 4 discloses a poly(meth)acrylate having a long-chain alkyl group and an alicyclic group as a peeling component. In particular, it is reported that it does not have active sites for cross-linking reaction by using together The poly(meth)acrylate and crosslinking agent form an interpenetrating polymer network structure to form a peeling layer with excellent heat resistance, solvent resistance, and substrate adhesion.

Prior art literature Patent literature Patent Document 1: Japanese Patent Application Publication No. 2004-306344 Patent Document 2: Japanese Patent Application Publication No. 2011-219630 Patent Document 3: Japanese Patent Application Publication No. 2003-300283 Patent Document 4: Japanese Patent Application Publication No. 2006-037069

Technical problem to be solved by the present invention Generally, in the production of a release layer using a crosslinking agent, after the release agent composition is applied to a substrate, the reactive functional groups of the constituent components in the composition form a crosslinked structure. However, in such a release agent composition, since the reactive functional groups start to react immediately after blending, the pot life (pot life) is shortened due to the gelation of the release agent composition, etc., resulting in production steps. The point of limitation, the point where the performance of the release layer may change with the passage of time after the release agent composition is blended, etc. become technical problems.

In addition, when a release sheet is used as a support for forming a material, it usually includes a step of applying the material on the release layer. In this step, if the release layer is shaved off due to contact with the parts of the coating device or solid particles in the material, the release layer components may be mixed into the material. Therefore, the release sheet is also required to have hardness.

The present invention was completed in view of the above-mentioned actual situation, and its object is to provide a release agent composition that can be prepared with a good pot life even when a crosslinking agent is used, and can produce a release agent composition with excellent peelability and hardness Release component (block copolymer) of the release sheet.

・・・(1) 通式(1)中，R¹ 為氫原子或甲基，R² 為碳原子數為1以上8以下的亞烷基。 [化學式2]

・・・(2) 通式(2)中，R³ 為氫原子或甲基，AO為碳原子數為2以上4以下的亞烷氧基，n為1以上30以下的亞烷氧基的平均加成莫耳數。 [化學式3]

・・・(3) 通式(3)中，R⁴ 為氫原子或甲基，R⁵ 為降冰片基、異冰片基、二環戊基、二環戊烯基、二環戊烯基氧基乙基或金剛烷基。 所述第二鏈段為由包含通式(4)所表示的含長鏈烷基單體的單體成分形成的聚合物鏈段。 [化學式4]

・・・(4) 通式(4)中，R⁶ 為氫原子或甲基，R⁷ 為碳原子數為12以上24以下的烷基。 在形成所述嵌段共聚物(A)的所有單體成分中，所述含羥基單體的比例為1質量%以上30質量%以下，所述含多環式脂肪族烴基單體的比例為5質量%以上45質量%以下，所述含長鏈烷基單體的比例為45質量%以上90質量%以下。Technical means to solve technical problems [01] The present invention relates to a block copolymer, which is a block copolymer (A) having a first segment and a second segment, wherein: the first segment is a monomer A polymer segment formed by a body component, the monomer component comprising at least one hydroxyl-containing monomer selected from the group consisting of a monomer represented by the general formula (1) and a monomer represented by the general formula (2) , And the polycyclic aliphatic hydrocarbon group-containing monomer represented by the general formula (3). [Chemical formula 1]

・・・(1) In the general formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is an alkylene group having 1 to 8 carbon atoms. [Chemical formula 2]

・・・(2) In the general formula (2), R ³ is a hydrogen atom or a methyl group, AO is an alkyleneoxy group with 2 to 4 carbon atoms, and n is an alkyleneoxy group with 1 to 30 The average number of bonus moles. [Chemical formula 3]

・・・(3) In the general formula (3), R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is norbornyl, isobornyl, dicyclopentyl, dicyclopentenyl, dicyclopentenyloxy Ethyl or adamantyl. The second segment is a polymer segment formed from a monomer component including a long-chain alkyl-containing monomer represented by the general formula (4). [Chemical formula 4]

・・・(4) In the general formula (4), R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is an alkyl group having 12 to 24 carbon atoms. Among all the monomer components forming the block copolymer (A), the ratio of the hydroxyl group-containing monomer is 1% by mass to 30% by mass, and the ratio of the polycyclic aliphatic hydrocarbon group-containing monomer is 5% by mass or more and 45% by mass or less, and the ratio of the long-chain alkyl group-containing monomer is 45% by mass or more and 90% by mass or less.

In addition, the present invention relates to a release layer formed from the release agent composition.

In addition, the present invention relates to a release sheet provided with the release layer on the surface of a substrate. Invention effect

Although the details of the mechanism of the effect of the block copolymer of the present invention have unexplained parts, it can be estimated as follows. However, the interpretation of the present invention may not be limited by this mechanism of action.

The block copolymer of the present invention has a first segment and a second segment. Since the first segment has a structure derived from the hydroxyl group-containing monomer, it is possible to introduce a crosslinked structure into the release layer by the reaction of the hydroxyl group of the block copolymer and the crosslinking agent, thereby improving the release layer The hardness. In addition, since the first segment has a structure derived from the polycyclic aliphatic hydrocarbon group-containing monomer, it can be extended by suppressing the proximity of the hydroxyl group of the block copolymer in the release agent composition to the crosslinking agent. valid period. Furthermore, since the second segment has a structure derived from the long-chain alkyl group-containing monomer, the releasability can be improved. Therefore, since the block copolymer of the present invention contains a specific amount of each of the above-mentioned monomer components, it is suitable as a peeling component as described below. The peeling component can be prepared with good properties even when a crosslinking agent is used. The release agent composition has a pot life, and can produce a release sheet with excellent releasability and hardness.

Hereinafter, the present invention will be described in detail. In addition, in the present invention, "(meth)acrylate" refers to a general term including both acrylate and methacrylate.

＜Block copolymer (A)＞ The block copolymer of the present invention is a block copolymer (A) having a first segment and a second segment.

・・・(1) 通式(1)中，R¹ 為氫原子或甲基，R² 為碳原子數為1以上8以下的亞烷基。 [化學式6]

・・・(2) 通式(2)中，R³ 為氫原子或甲基，AO為碳原子數為2以上4以下的亞烷氧基，n為1以上30以下的亞烷氧基的平均加成莫耳數。 [化學式7]

・・・(3) 通式(3)中，R⁴ 為氫原子或甲基，R⁵ 為降冰片基、異冰片基、二環戊基、二環戊烯基、二環戊烯基氧基乙基或金剛烷基。<First segment> The first segment is a polymer segment formed from a monomer component, and the monomer component includes a monomer selected from the group consisting of monomers represented by general formula (1) and those represented by general formula (2) One or more hydroxyl group-containing monomers in the monomer composition group, and the polycyclic aliphatic hydrocarbon group-containing monomer represented by the general formula (3). [Chemical formula 5]

・・・(1) In the general formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is an alkylene group having 1 to 8 carbon atoms. [Chemical formula 6]

・・・(2) In the general formula (2), R ³ is a hydrogen atom or a methyl group, AO is an alkyleneoxy group with 2 to 4 carbon atoms, and n is an alkyleneoxy group with 1 to 30 The average number of bonus moles. [Chemical formula 7]

・・・(3) In the general formula (3), R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is norbornyl, isobornyl, dicyclopentyl, dicyclopentenyl, dicyclopentenyloxy Ethyl or adamantyl.

In the general formula (1), R ² is an alkylene group having from 1 to 8 carbon atoms, which results in a difference in polarity from the long-chain alkyl group in the second segment and promotes the surface of the long-chain alkyl group. From the viewpoint of segregation, the number of carbon atoms is preferably 1 or more and 4 or less. As the monomer represented by the general formula (1), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate Among them, 2-hydroxyethyl (meth)acrylate is preferred.

In the general formula (2), AO is an alkyleneoxy group having 2 to 4 carbon atoms, and examples include ethyleneoxy (-C ₂ H ₄ O-) and propyleneoxy ( -C ₃ H ₆ O-), tetramethyleneoxy (-C ₄ H ₈ O-), etc. In the general formula (2), when -(AO)n- contains two or more kinds of alkyleneoxy groups, the arrangement of various alkyleneoxy groups may be block or random. In addition, in the general formula (2), n is the average number of added moles of alkyleneoxy groups of 1 or more and 30 or less. From the viewpoint of the introduction efficiency of hydroxyl groups in the block copolymer, n is preferably 1 Above 15 and below. As the monomer represented by the general formula (2), for example, ethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate , Polypropylene glycol mono(meth)acrylate, etc. At least one hydroxyl-containing monomer represented by the general formula (1) or the general formula (2) may be used, or two or more may be used in combination.

In the general formula (3), R ⁵ is norbornyl, isobornyl, dicyclopentyl, dicyclopentenyl, dicyclopentenyloxyethyl, or adamantyl, these organic groups It can be unsubstituted or substituted. As a substituent, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, etc. are mentioned, for example. As the polycyclic aliphatic hydrocarbon group-containing monomer represented by the general formula (3), for example, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, (meth) Dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc., among which isobornyl (meth)acrylate and (meth) Dicyclopentyl acrylate. At least one type of the polycyclic aliphatic hydrocarbon group-containing monomer represented by the general formula (3) may be used, or two or more types may be used in combination.

From the perspective of increasing the crosslinking density of the release layer and increasing the hardness, in the monomer components forming (constituting) the first segment, the hydroxyl-containing monomer is preferably 1% by mass or more, more preferably 5 Mass% or more, more preferably 10% by mass or more, and from the viewpoint of increasing the surface segregation of the block copolymer during the formation of the release layer and improving the release properties, the monomers forming (constituting) the first segment In the body composition, the hydroxyl-containing monomer is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.

From the viewpoint of suppressing the crosslinking reaction in the release agent composition and improving the pot life, among the monomer components forming (constituting) the first segment, the polycyclic aliphatic hydrocarbon group-containing monomer is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more, and from the viewpoint of increasing the crosslinking density of the release layer and increasing the hardness, the first segment is formed (constituted) Among the monomer components of, the polycyclic aliphatic hydrocarbon group-containing monomer is preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.

From the viewpoint of both the extension of the pot life brought about by the suppression of the crosslinking reaction and the increase in hardness brought about by the increase of the crosslinking density, in the monomer component forming (constructing) the first segment, the containing The total of the hydroxyl monomer and the polycyclic aliphatic hydrocarbon group-containing monomer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.

Among the monomer components that form (constitute) the first segment, in addition to the hydroxyl-containing monomer and the polycyclic fatty acid-containing monomer, in addition to satisfying the above-mentioned preferable ranges of the monomer components Other monomers other than group hydrocarbon monomers. The other monomers need only be known radically polymerizable monomers. From the viewpoint of the orientation control of the polycyclic alicyclic alkyl group, for example, those having a linear or branched chain having 1-24 carbon atoms are preferred. Alkyl-containing (meth)acrylates; those having fluorine-containing groups in which one or more hydrogen atoms of a linear or branched alkyl group having 1-12 carbon atoms are substituted by fluorine atoms ( Meth) acrylate; (meth) acrylate containing alkoxy terminal and polyalkylene glycol group, etc. As the linear or branched alkyl-containing (meth)acrylate having a carbon number of 1-24, for example, methyl (meth)acrylate, butyl (meth)acrylate, Dodecyl (meth)acrylate, stearyl (meth)acrylate, etc. As the fluorine-containing (meth)acrylate having a group in which one or more hydrogen atoms of a linear or branched alkyl group having 1-12 carbon atoms are substituted by fluorine atoms, for example, 1H, 1H, 2H, 2H-nonafluoron-hexyl (meth)acrylate, 1H, 1H, 2H, 2H-tridecafluoro-n-octyl, (meth)acrylate 1H, 1H, 2H, 2H-Heptadecafluoro-n-decyl ester and so on. As the (meth)acrylate containing an alkoxy group terminal and a polyalkylene glycol group, for example, poly(ethylene glycol) methyl ether (meth)acrylate can be cited. These other monomers can also be used in combination of two or more types.

・・・(4) 通式(4)中，R⁶ 為氫原子或甲基，R⁷ 為碳原子數為12以上24以下的烷基。<Second segment> The second segment is a polymer segment formed of a monomer component containing a long-chain alkyl group-containing monomer represented by the general formula (4). [Chemical formula 8]

・・・(4) In the general formula (4), R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is an alkyl group having 12 to 24 carbon atoms.

In the general formula (4), R ⁷ is an alkyl group having 12 or more and 24 or less carbon atoms. From the viewpoint of improving releasability, the number of carbon atoms is preferably 16 or more and 22 or less. As the long-chain alkyl-containing monomer represented by the general formula (4), for example, cetyl (meth)acrylate, stearyl (meth)acrylate, (meth) Eicosyl (meth)acrylate (icosyl (meth)acrylate), (docosyl (meth)acrylate), etc., among them, because of the ability to improve releasability, and because of the monomer Since it melts at 40°C or less and can shorten the melting time during production, stearyl (meth)acrylate is preferred. At least one type of the long-chain alkyl group-containing monomer represented by the general formula (4) may be used, or two or more types may be used in combination.

From the perspective of partially crystallizing long-chain alkyl groups with each other, reducing surface free energy, and improving releasability, among the monomer components that form (constitute) the second segment, the long-chain alkyl-containing monomer is more It is preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.

Among the monomer components forming (constituting) the second segment, in addition to satisfying the above-mentioned preferred range of the long-chain alkyl-containing monomer, it is also possible to use other than the long-chain alkyl-containing monomer Other monomers. The other monomer may be a known radically polymerizable monomer, but from the viewpoint of adjusting the peelability or the physical properties of the peeling layer, for example, it is preferably a linear or branched chain with 1-11 carbon atoms. Alkyl-containing (meth)acrylates; those having fluorine-containing groups in which one or more hydrogen atoms of a linear or branched alkyl group having 1-12 carbon atoms are substituted by fluorine atoms ( Meth)acrylate; (meth)acrylate containing alkoxy terminal and polyalkylene glycol group; (meth)acrylate containing reactive functional groups such as hydroxyl, epoxy, carboxyl, amino, etc. As the linear or branched alkyl group-containing (meth)acrylate having 1-11 carbon atoms, for example, methyl (meth)acrylate, butyl (meth)acrylate, Decyl (meth)acrylate and the like. As the fluorine-containing (meth)acrylate having a group in which one or more hydrogen atoms of a linear or branched alkyl group having 1-12 carbon atoms are substituted by fluorine atoms, for example, 1H, 1H, 2H, 2H-nonafluoron-hexyl (meth)acrylate, 1H, 1H, 2H, 2H-tridecafluoro-n-octyl, (meth)acrylate 1H, 1H, 2H, 2H-Heptadecafluoro-n-decyl ester and so on. As the (meth)acrylate containing an alkoxy group terminal and a polyalkylene glycol group, for example, poly(ethylene glycol) methyl ether (meth)acrylate can be cited. As the reactive functional group-containing (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid, etc. are preferred. These other monomers can also be used in combination of two or more types.

Among all the monomer components forming the block copolymer (A), the ratio of the hydroxyl group-containing monomer is 1% by mass to 30% by mass. From the perspective of increasing the crosslinking density of the release layer and increasing the hardness, among all monomer components forming the block copolymer (A), the ratio of the hydroxyl-containing monomer is preferably 5% by mass or more, and more It is preferably 10% by mass or more, and from the viewpoint of increasing the surface segregation of the block copolymer during the formation of the release layer and improving the releasability, among all the monomer components forming the block copolymer (A), The ratio of the hydroxyl-containing monomer is preferably 25% by mass or less, and more preferably 20% by mass or less.

Among all the monomer components forming the block copolymer (A), the ratio of the polycyclic aliphatic hydrocarbon group-containing monomer is 5% by mass or more and 45% by mass or less. From the viewpoint of suppressing the crosslinking reaction in the release agent composition and improving the pot life, among all the monomer components forming the block copolymer (A), the ratio of the polycyclic aliphatic hydrocarbon group-containing monomer It is preferably 10% by mass or more, more preferably 15% by mass or more, and from the viewpoint of increasing the crosslinking density of the release layer and increasing the hardness, among all the monomer components forming the block copolymer (A) The proportion of the polycyclic aliphatic hydrocarbon group-containing monomer is preferably 40% by mass or less, more preferably 35% by mass or less.

Among all the monomer components forming the block copolymer (A), the ratio of the long-chain alkyl group-containing monomer is 45% by mass or more and 90% by mass or less. From the perspective of partially crystallizing long-chain alkyl groups with each other, reducing surface free energy, and improving releasability, among all the monomer components forming the block copolymer (A), the long-chain alkyl group-containing monomer The ratio is preferably 50% by mass or more, more preferably 55% by mass or more, and from the viewpoint of both increasing the crosslinking density of the release layer and increasing the pot life, all the blocks forming the block copolymer (A) In the monomer components, the ratio of the long-chain alkyl group-containing monomer is preferably 85% by mass or less, more preferably 80% by mass or less.

Among all the monomer components forming the block copolymer (A), the ratio of the monomer components forming the first segment is preferably 10% by mass or more and 50% by mass or less. From the viewpoint of increasing the crosslinking density of the release layer and increasing the hardness, among all the monomer components forming the block copolymer (A), the ratio of the monomer components forming the first segment is more preferably 20 % By mass or more, preferably 30% by mass or more, and from the viewpoint of improving releasability, among all monomer components forming the block copolymer (A), the monomer forming the first segment The ratio of the components is more preferably 47% by mass or less, and still more preferably 45% by mass or less.

＜Preparation method of block copolymer (A)＞ The preparation method of the block copolymer (A) of the present invention can use known preparation methods of block copolymers without any limitation. For example, anionic polymerization method and polymerization using polymeric peroxide can be cited. Law etc. Examples of the polymerization method include a bulk polymerization method, a suspension polymerization method, a solution polymerization method, and an emulsion polymerization method.

・・・(5) 通式(5)中，m表示1-10的整數，n表示2-20的整數。 [化學式10]

・・・(6) 通式(6)中，n表示2-20的整數。 [化學式11]

・・・(7) 通式(7)中，n表示2-20的整數。The polymerization method using a macromolecular peroxide is a polymerization method in which a compound having two or more peroxy (peroxide) bonds in one molecule is used as a polymerization initiator. As the macromolecular peroxide, for example, various macromolecular peroxide compounds disclosed in Japanese Patent Publication No. 5-59942 can be cited. At least one type of the macromolecular peroxide may be used, or two or more types may be used in combination. [02] As the macromolecular peroxide, preferably: a compound having a structure represented by the general formula (5), a compound having a structure represented by the general formula (6), a compound having a structure represented by the general formula (7) The structure of the compound. [Chemical formula 9]

・・・(5) In the general formula (5), m represents an integer of 1-10, and n represents an integer of 2-20. [Chemical formula 10]

・・・(6) In the general formula (6), n represents an integer of 2-20. [Chemical formula 11]

・・・(7) In the general formula (7), n represents an integer of 2-20.

The polymerization method using the macromolecular peroxide is, for example, a polymerization method including a first step and a second step. In the first step, the macroperoxide is used as a polymerization initiator to make the general formula (4) The step of polymerizing the long-chain alkyl-containing monomer in a solution (polymerization solvent), thereby obtaining a solution of a polymer having a peroxy bond-containing second segment in which a peroxy bond is introduced into the chain In this second step, the hydroxyl-containing monomer represented by the general formula (1) or (2) and the general formula are added to the obtained solution of the polymer having the second segment of the peroxy bond (3) The step of polymerizing and polymerizing the polycyclic aliphatic hydrocarbon group-containing monomer, thereby obtaining the block copolymer (A) composed of the first segment and the second segment. In addition, in the polymerization method using macromolecular peroxides, the following operations can also be performed: as the first step, add the hydroxyl-containing monomer represented by the general formula (1) or (2) and The polycyclic aliphatic hydrocarbon group-containing monomer represented by the general formula (3) obtains a solution of the polymer having the first segment of the peroxy bond, and then as the second step, the general formula (4) is added The long-chain alkyl-containing monomers represented are polymerized.

The said solution (polymerization solvent) should just be a solution which can prepare a block copolymer (A). As the solution (polymerization solvent), for example, acetone, 2-butanone, 3-methyl-2-butanone, 2-pentanone, 3-pentanone, 2-methyl-3-pentanone , 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2-hexyl Ketone, 3-hexanone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-hexanone, 5-methyl-2-hexanone, Ketone solvents such as 5-methyl-3-hexanone; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl trimethyl acetate, isobutyl acetate, sec-butyl acetate Ester, amyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, tert-butyl propionate, isobutyl propionate, butyl Methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl isobutyrate, methyl 2-methyl butyrate, methyl caproate, cellosolve acetate Ester solvents such as benzene, toluene, ethylbenzene, xylene, phenol, cyclohexane, hexane, isohexane, isohexene, heptane, octane, isooctane, nonane, isononane, decane, Undecane, dodecane, tridecane, isoalkane solvents (manufactured by NOF CORPORATION, trade names: NAS-3, NAS-4, NAS-5H) and other hydrocarbon solvents; formamide, acetamide , Dimethylformamide, dimethylacetamide, acetonitrile and other nitrogen-containing solutions; 1,1,2,-trifluoro-1,2,2-trichloroethane, tetrachlorodifluoroethane, Halogen solvents such as methyl chloroform, hexafluoroisopropanol, (methyl)p-difluorotoluene, perfluorohexane, perfluoroheptane, etc.; dimethyl sulfoxide, tetrahydrofuran, etc. The said solution (polymerization solvent) can also be used in combination of 2 or more types.

In addition, the amount of the macroperoxide used is preferably 0.5-20 parts by mass, more preferably 2-15 parts by mass relative to 100 parts by mass of the monomer components constituting the block copolymer (A). The temperature for the polymerization reaction can be appropriately changed according to the type of the macromolecular peroxide used, but in the case of industrial production, it is preferably 30-150°C, more preferably 40-100°C.

The weight average molecular weight (Mw) of the block copolymer (A) is preferably 5,000 or more and 200,000 or less, more preferably 8,000 or more and 150,000 or less, and still more preferably 10,000 or more and 100,000 or less. In addition, the weight average molecular weight (Mw) can be obtained under the following conditions. If the weight average molecular weight is less than 5,000, there is a possibility that the difference in the composition ratio of the monomer components of each block copolymer becomes large, and the releasability decreases. On the other hand, if the weight average molecular weight exceeds 200,000, the solubility may be insufficient when preparing the release agent composition.

<Measurement conditions of weight average molecular weight (Mw)> Analysis device: TOSOH HLC-8320GPC Column: TSKgel SuperMulbipore HZ-M (manufactured by TOSOH CORPORATION) Eluent: THF Flow rate: 0.35ml/min Detector: RI Chromatographic column temperature: 40 ℃ Sample concentration: 0.2 wt% Sample injection volume: 10 μL Standard sample: Standard polystyrene

＜Release agent composition＞ The release agent composition of the present invention contains the block copolymer (A) and a crosslinking agent (B) having a functional group reactive with a hydroxyl group.

The crosslinking agent (B) having a functional group reactive with a hydroxyl group may be a crosslinking agent having a functional group showing reactivity with the hydroxyl group of the block copolymer (A). As the crosslinking agent (B), for example, from the viewpoint of obtaining a strong release layer, isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, and oxazolines are preferred Type crosslinking agent, melamine type crosslinking agent, more preferably isocyanate type crosslinking agent. The crosslinking agent (B) may be used in combination of two or more kinds.

As the isocyanate crosslinking agent, for example, polyisocyanates such as aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates; biuret and isocyanate of the polyisocyanate Urate body and adducts as reactants with low molecular weight active hydrogen compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc.

As the polyisocyanate, for example, diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, trimethylene diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate can be cited. , Isophorone diisocyanate, trimethylhexamethylene diisocyanate; their isocyanurate, or their polymethylene polyphenyl polyisocyanate, etc. Among them, hexamethylene diisocyanate, polyisocyanurate composed of hexamethylene diisocyanate, and polyisocyanate obtained by the reaction of hexamethylene diisocyanate and polyol are preferred.

It is preferable to add the crosslinking agent (B) so that the total amount of the functional groups that can react with the crosslinking agent (B) in the release agent composition is about 0.5-1.5 mol relative to the functional group of the crosslinking agent (B). B), it is more preferable to add the crosslinking so that the total amount of the functional groups of the crosslinking agent (B) with respect to the functional groups that can react with the crosslinking agent (B) in the release agent composition is about 0.8-1.2 mol剂(B).

Further, from the viewpoint of imparting functions other than peelability, such as chemical resistance, oil resistance, and scratch resistance, to the peeling layer, the peeling agent composition of the present invention may include a peeling agent that reacts with the crosslinking agent (B). Functional polymer (C).

The polymer (C) having a functional group reactive with the crosslinking agent (B) should be a polymer having a functional group (reactive functional group) showing reactivity with the functional group of the crosslinking agent (B). can. Examples of the reactive functional group include hydroxyl, carboxyl, amino, etc., which are less likely to cause proton exchange reactions when they remain in the peeling layer after the crosslinking reaction, and have little adverse effects on objects in contact with the peeling layer. , Preferably hydroxyl. For the polymer (C), from the perspective of improving the durability of the release layer, the total reactive functional group value (reactive functional group) of 1 g of the polymer (C) is preferably 20-200 mg/KOH About, more preferably about 30-160 mg/KOH. In addition, as the polymer, for example, poly(meth)acrylic resins, polyvinyl acetate resins, polyvinyl ether resins, polyester resins, urethane resins, fluororesins, and polyurethane resins can be cited. Alkyl glycol, polyalkylene imine, methyl cellulose, hydroxy cellulose, starches, etc., among them, fluororesin is preferred. The polymer (C) may be used in combination of two or more kinds.

The fluororesin is a copolymer containing fluoroolefin as a structural unit. As the fluoroolefin, tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), perfluoro (alkyl vinyl ether), trifluoroethylene, vinylidene fluoride ( VdF), vinyl fluoride, etc. The fluoroolefin may be used in combination of two or more kinds.

In addition, in the fluororesin, as a structural unit, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether can be used Hydroxyalkyl vinyl ethers such as diethylene glycol monovinyl ether; ethylene glycol monovinyl ethers such as diethylene glycol monovinyl ether; 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and other hydroxyalkyl groups Allyl ethers; vinyl hydroxyalkanoates such as vinyl glycolate and vinyl hydroxybutyrate; allyl hydroxyalkanoates such as allyl glycolate; hydroxyethyl (meth)acrylate, etc. Hydroxyalkyl (meth)acrylates and other hydroxyl-containing monomers. In addition, vinyl ethyl ether, n-propyl vinyl ether, n-butyl vinyl ether, octadecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether and other alkyl vinyl groups can also be used. Ethers; vinyl carboxylates such as vinyl propionate and vinyl butyrate; alkyl allyl ethers such as ethyl allyl ether, n-propyl allyl ether and n-butyl allyl ether; Allyl carboxylates such as allyl propionate and allyl butyrate; (meth)acrylates such as ethyl methacrylate and propyl methacrylate; polyolefins such as ethylene, propylene, n-butene, and isobutylene; Aromatic group-containing monomers such as vinyl benzoate and vinyl 4-tert-butyl benzoate.

In the release agent composition, when the polymer (C) is used, it is from the viewpoint of both the releasability due to the block copolymer and the chemical resistance due to the polymer , With respect to 100 parts by mass of the block copolymer (A), the polymer (C) is preferably 25 parts by mass or more, more preferably 50 parts by mass or more, and preferably 900 parts by mass or less, more It is preferably 400 parts by mass or less.

The release agent composition can be prepared by diluting with an organic solvent. As the organic solvent, the same solvents as those exemplified as the polymerization solvent can be used. The solid content concentration of the release agent composition is usually about 0.1-50% by mass, preferably about 1-20% by mass.

The release agent composition may use curing catalysts, pH adjusters, preservatives, ultraviolet absorbers, antioxidants, light stabilizers, rheology adjusters, antistatic agents, organic particles, inorganic particles, and coloring as needed. Agent, flame retardant, leveling agent, etc.

＜Peeling layer＞ The release layer of the present invention is formed of the release agent composition, and can be produced, for example, by coating the release agent composition (solution) on a substrate, and then drying and removing the solvent to form it on the substrate. As the coating method, various conventionally known methods can be used. For example, gravure coating, roll coating, blade coating, knife coating, bar coating, spray coating, spin coating, etc. can be used. The drying preferably adjusts the drying temperature and time appropriately according to the solvent, crosslinking agent (B), etc. used, and it is usually about 60-200°C for 10 seconds to 10 minutes. In addition, the drying can also be combined with different drying conditions.

As the substrate, plastic substrates such as acrylic resin, polyester resin, polycarbonate resin, triacetate cellulose resin, polyethylene terephthalate resin, etc. can be cited; high-quality paper , Coated paper and other paper substrates. The shape of the substrate is not particularly limited, but a film or sheet is preferred from the viewpoint of a suitable form as a release sheet. In addition, various functional layers such as a primer layer and an adhesive layer; surface treatment layers such as corona treatment, UV ozone treatment, plasma treatment, etc. may also be appropriately provided between the substrate and the release layer.

From the viewpoint of manufacturability or function-imparting, the film thickness of the release layer is preferably 0.01-100 μm, more preferably 0.1-10 μm.

＜Peeling piece＞ The release sheet of the present invention may provide the release layer on the surface of the substrate. As the peeling sheet, for example, the use of protecting a support, an adhesive layer, etc. of materials used to form green sheets of synthetic leather or electronic materials, etc. can be cited.

Example [03] Hereinafter, the present invention will be further described in detail through embodiments, but the present invention is not limited by these embodiments.

<Preparation of block copolymer (A)>

<Example 1> 73.9 g of toluene was added to a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, and it was heated to 70°C while blowing in nitrogen. Then, maintaining the temperature and nitrogen atmosphere in the reaction vessel, 9.0 g of 2-hydroxyethyl methacrylate, 25.0 g of dicyclopentyl methacrylate, and 1.0 g of methyl methacrylate were simultaneously added over 1 hour. , 106.4 g of toluene mixture, and 16.7 g of polymerization initiator solution composed of macromolecular peroxide (n=10) having the structure represented by the general formula (7), and then polymerize for 3 hours The reaction yields a polymer solution with a first segment containing a peroxy bond. Next, a mixed solution of 65.0 g of stearyl methacrylate and 22.3 g of toluene was added over 1 hour, and the polymerization reaction was performed for 2 hours. Then, the temperature was further raised to 80°C and the polymerization reaction was performed for 3 hours to obtain a polymerization solution containing a block copolymer (A) having a first segment and a second segment. The obtained polymerization solution was diluted with toluene to obtain a solution (solid content concentration of 30% by mass) containing the block copolymer (A). The analysis based on the above-mentioned GPC measurement method revealed that Mw was 53,000 and Mw/Mn was 3.4.

<Example 1-7, Comparative Example 1-2> In each of the Examples and Comparative Examples, except that the monomer components and their blending amounts described in Example 1 were changed to those shown in Table 1, the same operations as in Example 1 were performed to obtain Examples 1-7, The solution containing the block copolymer (A) of Comparative Example 1-2. In addition, based on the above method, Mw and Mw/Mn were measured. The results are shown in Table 1.

<Preparation of random copolymer>

<Comparative Example 3> Add 106.4 g of toluene to a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, and heat to 70°C while blowing in nitrogen. Then, maintaining the temperature and nitrogen atmosphere in the reaction vessel, 20.0 g of 2-hydroxyethyl methacrylate, 25.0 g of dicyclopentyl methacrylate, and 55.0 g of octadecyl methacrylate were simultaneously added over 1 hour. A mixture of alkyl ester, 88.1 g of toluene, and 2.2 g of bis(3,5,5-trimethylhexyl) peroxide (product name: PEROYL355, manufactured by NOF CORPORATION), 22.0 g The polymerization initiator solution composed of toluene was further conducted for 9 hours to obtain a polymerization solution containing a random copolymer. The obtained polymerization solution was diluted with toluene to obtain a solution containing a random copolymer (solid content concentration: 30% by mass). The analysis based on the above-mentioned GPC measurement method revealed that Mw was 46,000 and Mw/Mn was 3.2.

<Comparative example 4-5> In each comparative example, except that the monomer components described in Comparative Example 3 and their blending amounts were changed to those shown in Table 2, the same operation as in Comparative Example 3 was performed to obtain the inclusion random of Comparative Example 4-5 Copolymer solution. In addition, based on the above method, Mw and Mw/Mn were measured. The results are shown in Table 2.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example 1 Comparative example 2 Block copolymer (A) First segment Hydroxyl-containing monomer (parts by mass) HEMA 9 20 14 7 17 18 25 2 50PET800 20 Monomers containing polycyclic aliphatic hydrocarbon groups (parts by mass) DCPMA 25 25 25 26 32 25 35 3 iBorA 6 27 Other monomers MMA 1 Second segment Long-chain alkyl monomer (parts by mass) SMA 65 55 55 60 55 54 49 40 95 Other monomers (parts by mass) BMA 5 HEMA 4 1 Mw(×10,000) 5.3 5.1 5.8 4.4 5.4 5.5 5.5 5.1 6.5 Mw/Mn 3.4 3.5 4.1 3.7 3.5 3.6 3.9 3.8 3.7

[Table 2] Comparative example 3 Comparative example 4 Comparative example 5 Random copolymer Hydroxyl-containing monomer (parts by mass) HEMA 20 20 20 Monomers containing polycyclic aliphatic hydrocarbon groups (parts by mass) DCPMA 25 80 Long-chain alkyl monomer (parts by mass) SMA 55 80 Mw(×10,000) 4.6 4.5 5.3 Mw/Mn 3.2 3.2 3.7

In Table 1 and Table 2: HEMA stands for 2-hydroxyethyl methacrylate; 50PET800 represents polyethylene glycol-tetramethylene glycol-monomethacrylate (BLEMMER 55PET-800, manufactured by NOF CORPORATION. The average added mole number of ethylene oxide is 10, tetramethylene oxide The average added mole number of the group is 5, and the arrangement of the ethyleneoxy group and the tetramethyleneoxy group is a block); DCPMA stands for dicyclopentyl methacrylate; iBorA means isobornyl acrylate; MMA stands for methyl methacrylate; SMA stands for stearyl methacrylate (stearate methacrylate); BMA stands for n-butyl methacrylate.

<Example 1-1>

<Preparation of release agent composition> 27.2 g of the block copolymer (A)-containing solution (solid content: 30.0% by mass, solvent: toluene) obtained in Example 1 above, and 2.4 g of isocyanate as the crosslinking agent (B) were crosslinked (Trade name: "CORONATEL", manufactured by TOSOH CORPORATION), 0.6 g of a 0.01% by mass toluene solution of dibutyltin dilaurate as a curing catalyst, and 69.8 g of toluene were mixed to obtain a release agent composition. The following evaluations were performed on the obtained release agent composition. The results are shown in Table 3.

＜Evaluation of pot life＞ For evaluation of pot life, use a cone-plate viscometer (measuring device: TVE-25L (manufactured by TOKI SANGYO CO., LTD.), measurement temperature: 25 ℃, rotor type: standard type) to measure the initial viscosity of the release agent composition After that, the time until the viscosity of the release agent composition after standing at 25°C exceeds twice the initial viscosity is regarded as the pot life for evaluation.

＜Manufacture of release sheet＞ For the release agent composition obtained above, the release agent composition was coated on a PET film (trade name: "A4300", TOYOBO) using a bar coater (No. 02, manufactured by Daiichi Rika Co., Ltd., wet film thickness: 4.6 μm) CO., LTD. (manufactured by CO., LTD.) after mounting, it was heated and cured in a blast oven at 100°C for 5 minutes to produce a release sheet. The following evaluation method was performed on the obtained release sheet. The results are shown in Table 3.

＜Evaluation of peelability＞ Regarding the evaluation of peelability, an acrylic adhesive tape (manufactured by NITTO DENKO CORPORATION, model: 31B, width 25 mm) was attached to the surface of the peeling layer of the peeling sheet to produce a test piece, and the temperature was 25°C and 60%RH After leaving for 24 hours, using a tensile tester (measuring device: AGS-H 500N (manufactured by Shimadzu Corporation), tensile speed: 200 mm/min, tensile angle: 180°), the adhesive tape was measured from the obtained test The peeling force from the sheet was measured and evaluated by the peeling force (N). In addition, the peeling force (N) is the average value of three different test pieces.

＜Evaluation of hardness＞ Regarding the evaluation of hardness, according to JIS K5600-5-4 (apparatus: metal block with wheels based on JIS K5600-5-4, contact angle between the coating film and the pencil: 45°, load: 750 g, pencil: product The name "Uni" (manufactured by MITSUBISHIPENCIL CO., LTD.), the number of tests: each pencil hardness is twice) The pencil hardness test is performed on the surface of the peeling layer of the peeling sheet, and the pencil hardness of the hardest pencil that has no scratches is taken as the pencil hardness Hardness and evaluation.

<Example 1-2-7-1, Comparative Example 1-1-5-1>

<Preparation of release agent composition, and manufacture of release sheet> In each of the Examples and Comparative Examples, the same operation as in Example 1 was performed, except that the types of raw materials and their blending amounts were changed to those shown in Table 3 or Table 4. After obtaining the release agent composition and the release sheet , Perform the same evaluation as above. The evaluation results are shown in Table 3 and Table 4.

[table 3] Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 2-1 Example 2-2 Example 3-1 Example 4-1 Example 5-1 Example 6-1 Example 7-1 Stripper composition Block copolymer (A) (parts by mass) Example 1 27.2 14.3 8.5 14 Example 2 25.5 8.2 Example 3 8.7 Example 4 8.4 Example 5 8.6 Example 6 8.2 Example 7 8.2 Crosslinking agent (B) (parts by mass) CL 2.4 C-HX 1.4 1.5 1.6 2.4 1.8 1.3 1.6 1.4 1.8 1.8 Polymer (C) (parts by mass) LF200 7.2 10 9.5 10.2 9.8 10 9.5 9.6 LF910LM 6.4 DBTtol (parts by mass) 0.6 0.5 0.5 0.5 0.8 0.6 0.6 0.5 0.5 0.6 0.6 Toluene (parts by mass) 69.8 76.6 79.5 77.5 71.3 79.9 79.2 79.7 79.5 79.9 79.8 Evaluation Applicable period (hours) twenty four 16 16 12 16 12 10 14 18 8 10 Peelability (N) 0.2 0.2 0.2 0.2 0.3 0.3 0.3 0.3 0.2 0.4 0.7 hardness HB HB HB H H H HB HB B H H

[Table 4] Comparative example 1-1 Comparative example 2-1 Comparative example 3-1 Comparative example 4-1 Comparative example 5-1 Stripper composition Block copolymer (A), or random copolymer (parts by mass) Comparative example 1 8 Comparative example 2 8.8 Comparative example 3 8.2 Comparative example 4 8.2 Comparative example 5 8.2 Crosslinking agent (B) (parts by mass) C-HX 2 1.2 1.8 1.8 1.8 Polymer (C) (parts by mass) LF200 9.4 10.2 9.5 9.5 9.5 DBTtol (parts by mass) 0.7 0.4 0.7 0.7 0.7 Toluene (parts by mass) 79.9 79.4 79.8 79.8 79.8 Evaluation Applicable period (hours) 8 ＞200 4 10 4 Peelability (N) 5.9 0.2 16.2 16.1 2.8 hardness H 3B H HB HB

In Table 3 and Table 4: C-L represents isocyanate crosslinking agent (trade name: "CORONATE L", manufactured by TOSOH CORPORATION, solid content: 74-76 mass%, NCO content: 12.7-13.7 mass%); C-HX means isocyanate crosslinking agent (trade name: "CORONATE HX", HDI polyisocyanate, manufactured by TOSOH CORPORATION, solid content: 100% by mass, NCO content: 20.5-22.0% by mass); LF200 represents a hydroxyl-containing fluororesin (trade name: "LUMIFLON LF200", solid content: 60% by mass, hydroxyl value: 31 mg(KOH)/g, manufactured by AGC CHEMICALS); LF910LM represents a hydroxyl-containing fluororesin (trade name: "LUMIFLON LF910LM", solid content: 65% by mass, hydroxyl value: 63-73 mg(KOH)/g, manufactured by AGC CHEMICALS); DBTtol represents a 0.01% by mass toluene solution of dibutyltin dilaurate.

no

Claims (8)

A block copolymer, which is a block copolymer (A) having a first segment and a second segment, characterized in that the first segment is a polymer segment formed by monomer components, and The monomer component includes one or more hydroxyl-containing monomers selected from the group consisting of a monomer represented by the general formula (1) and a monomer represented by the general formula (2) and a hydroxyl-containing monomer represented by the general formula (3) Polycyclic aliphatic hydrocarbon monomers, [Chemical formula 1]

・・・(1) In the general formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is an alkylene group having 1 to 8 carbon atoms, [Chemical formula 2]

・・・(2) In the general formula (2), R ³ is a hydrogen atom or a methyl group, AO is an alkyleneoxy group with 2 to 4 carbon atoms, and n is an alkyleneoxy group with 1 to 30 Average number of added moles, [Chemical formula 3]

・・・(3) In the general formula (3), R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is norbornyl, isobornyl, dicyclopentyl, dicyclopentenyl, dicyclopentenyloxy The second segment is a polymer segment formed from a monomer component containing a long-chain alkyl-containing monomer represented by the general formula (4), [Chemical formula 4]

・・・(4) In the general formula (4), R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is an alkyl group having 12 or more and 24 or less carbon atoms. All of the blocks forming the block copolymer (A) In the monomer components, the proportion of the hydroxyl-containing monomer is 1% by mass to 30% by mass, the proportion of the polycyclic aliphatic hydrocarbon group-containing monomer is 5% by mass to 45% by mass, and the length-containing monomer The ratio of the alkyl monomer is 45% by mass or more and 90% by mass or less. The block copolymer according to claim 1, wherein among all monomer components forming the block copolymer (A), the ratio of the monomer components forming the first segment is 10 mass % Above 50% by mass. A release agent composition characterized by comprising the block copolymer (A) described in claim 1 or 2 and a crosslinking agent (B) having a functional group reactive with a hydroxyl group. The release agent composition according to claim 3, wherein the crosslinking agent (B) is an isocyanate crosslinking agent. The release agent composition according to claim 3 or 4, further comprising a polymer (C) having a functional group reactive with the crosslinking agent (B). The release agent composition according to claim 5, wherein the polymer (C) is a hydroxyl-containing fluororesin. A peeling layer characterized in that it is formed of the peeling agent composition according to any one of claims 3-6. A release sheet, characterized in that the release layer according to claim 7 is provided on the surface of a substrate.