JP4409476B2 - Release agent composition and release material - Google Patents

Description

  The present invention relates to a release agent composition and a release material. More specifically, the present invention relates to a release agent composition containing a poly (meth) acrylic acid ester as a main agent and, if necessary, a crosslinking agent, and a release material having a release layer made of the composition on a substrate.

  Conventionally, a pressure-sensitive adhesive sheet has been used in the manufacturing process of semiconductor devices and the like. Usually, the pressure-sensitive adhesive layer of such a pressure-sensitive adhesive sheet has a release agent composition containing a silicone compound on the substrate in order to protect the pressure-sensitive adhesive layer. A release material having a release layer made of a product is laminated.

  However, since the silicone compound generally has a property of easily transferring, in the semiconductor field, when such an adhesive sheet is used, the silicone compound constituting the release layer is transferred to the adhesive layer, and the semiconductor device. It is thought that this causes a malfunction of the circuit. Therefore, there is a demand for a release material having a release layer made of a release agent that does not contain a silicone compound.

  Examples of such release agents that do not contain a silicone compound include alkyd resin release agents, olefin resin release agents, and acrylic resin release agents having a long chain alkyl group (hereinafter also referred to as “long chain alkyl release agents”). Has been proposed (see, for example, Patent Documents 1 to 3).

However, the alkyd resin release agent has a problem that its application is limited due to its high release force, and the olefin resin release agent cannot form an adhesive layer on the release material because of its poor heat resistance. The long-chain alkyl-based release agent is poor in workability such as white turbidity and unevenness at the time of coating because the long-chain alkyl-based resin has low solubility in the coating solvent in which the long-chain alkyl-based resin is generally used. In addition, there is a problem that adhesion to a substrate such as a film is poor.
JP 2003-183619 A JP 2003-147327 A JP 2000-290610 A

  An object of the present invention is to provide an acrylic resin-based release agent containing an alicyclic group that is excellent in solubility, heat resistance, and substrate adhesion without adversely affecting electronic components and the like and capable of adjusting the release force. It is providing the release material which has a peeling layer which consists of a composition and this composition.

  As a result of intensive studies in view of the above problems, the present inventors have improved the processability of the release agent composition by using a poly (meth) acrylate ester having an alicyclic group that is highly soluble in a coating solvent. In addition, it has been found that a release layer excellent in heat resistance, substrate adhesion and release performance can be formed.

  That is, the release agent composition according to the present invention includes (A) a poly (meth) acrylic acid ester containing a structural unit represented by the following general formula (1).

In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alicyclic group having 5 to 18 carbon atoms, and the alicyclic group may contain an oxygen atom or a nitrogen atom. .
The poly (meth) acrylic acid ester (A) is in the range of 0 to 300 parts by weight of the structural unit represented by the following general formula (2) with respect to 100 parts by weight of the structural unit represented by the general formula (1). It may contain.

In Formula (2), R ¹ represents a hydrogen atom or a methyl group, R ³ represents an alkyl group having 1 to 28 carbon atoms or an aromatic group, and the alkyl group contains a fluorine atom, an oxygen atom, or a nitrogen atom. May be.

  The poly (meth) acrylic acid ester (A) has 0 structural units derived from a (meth) acrylic acid ester having a reactive functional group with respect to 100 parts by weight of the structural unit represented by the general formula (1). You may contain in the range of -50 weight part.

The poly (meth) acrylic acid ester (A) may have a side chain containing a double bond.
The release agent composition of the present invention may further contain a cross-linking agent (B), and the cross-linking agent (B) is added to the poly (meth) acrylic acid ester (A) in an amount of 0.1 parts by weight. It is desirable to contain in the range of 01 to 230 parts by weight. Examples of such a crosslinking agent (B) include urethane compounds, urea compounds, amide compounds, amino resins, and energy ray curable compounds.

  The release material according to the present invention is characterized in that it has a release layer composed of the release agent composition on at least one side of a substrate.

  Since the release agent composition of the present invention uses an alicyclic group-containing poly (meth) acrylic acid ester having high solubility in a coating solvent as a main agent, it does not cause white turbidity or unevenness at the time of application, In addition to excellent processability, a release layer having excellent substrate adhesion and heat resistance can be formed.

Further, according to the present invention, when a semi-IPN (interpenetrating polymer network) structure is formed by using a poly (meth) acrylic acid ester having no active site for a crosslinking reaction and a crosslinking agent, Since the degree of freedom of the side chain of (meth) acrylic acid ester is ensured, the surface energy of the release layer can be lowered, and the adhesive strength with the substrate side can be designed to be high. Can be formed.

  Furthermore, according to the present invention, since the peeling force can be adjusted by selecting a monomer to be copolymerized with the poly (meth) acrylic acid ester as the main agent, it is possible to provide a release material according to various applications. it can.

  In addition, according to the present invention, since a silicone compound is not used, even if an adhesive sheet or the like on which the release material of the present invention is laminated is used in a manufacturing process of an electronic component such as a semiconductor device, There is no risk of adverse effects on parts.

Hereinafter, the release agent composition according to the present invention and the release material having a release layer comprising the composition will be described in detail.
[Release composition]
The release agent composition according to the present invention contains (A) poly (meth) acrylic acid ester as a main agent. In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid.

(A) Poly (meth) acrylic acid ester In the release agent composition of the present invention, the poly (meth) acrylic acid ester (hereinafter also referred to as “polymer (A)”) used as the main agent is represented by the following general formula (1). (Hereinafter also referred to as “structural unit (1)”).

In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alicyclic group having 5 to 18 carbon atoms, and the alicyclic group may contain an oxygen atom or a nitrogen atom. May be monocyclic or polycyclic. By having such an alicyclic group, the solubility in a coating solvent can be improved as compared with the case of a long-chain alkyl group, and it has a peeling performance comparable to that of a long-chain alkyl group. A release layer can be formed.

As the monomer that can be the structural unit (1) (hereinafter also referred to as “monomer (1)”), (meth) acrylic acid ester in which the ester portion is an alicyclic group having 5 to 18 carbon atoms is used. For example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 3-oxocyclohexyl (meth) acrylate, butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Adamantyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate, (R)-(t) -α-acryloyloxy-β , Β-Dimethyl-γ-butyrolacto And the like. These may be used alone or in combination of two or more.

Among the monomers (1), cyclohexyl (meth) acrylate, butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate are preferred because of good solubility and polymerizability.

  In addition to the structural unit (1), the polymer (A) may contain a structural unit represented by the following general formula (2) (hereinafter also referred to as “structural unit (2)”). .

In Formula (2), R ¹ represents a hydrogen atom or a methyl group, R ³ represents an alkyl group having 1 to 28 carbon atoms or an aromatic group, and the alkyl group contains a fluorine atom, an oxygen atom, or a nitrogen atom. May be.

  As the monomer that can be the structural unit (2) (hereinafter also referred to as “monomer (2)”), the ester moiety is an alkyl group having 1 to 28 carbon atoms (fluorine atom, oxygen atom, or nitrogen atom). And (meth) acrylic acid ester which is an aromatic group.

Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate , Isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (Meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) Chryrate, docosyl (meth) acrylate, tetracosyl (meth) acrylate, hexacosyl (meth) acrylate, octacosyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (Meth) acrylate, 1H,
1H-perfluoro-n-octyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, ethylene glycol methyl ether (meth) acrylate , 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, ethyl 3-benzoyl acrylate, furfuryl methacrylate, and the like. These may be used alone or in combination of two or more.

  The content of the structural unit (2) in the polymer (A) is usually 0 to 300 parts by weight, preferably 0.5 to 100 parts by weight, more preferably 100 parts by weight of the structural unit (1). Is 10 to 100 parts by weight. By including the structural unit (2) in an amount within the above range in the polymer (A), the peeling force of the release layer comprising the release agent composition containing the polymer (A) can be adjusted.

The polymer (A) may contain a structural unit derived from a (meth) acrylic acid ester containing a reactive functional group (hereinafter also referred to as “structural unit (3)”). Examples of such reactive functional groups include hydroxyl groups, amino groups, carboxyl groups, epoxy groups, vinyl groups, allyl groups, chloro groups, and thiol groups. Such reactive functional groups may be contained singly or in combination of two or more. Among the reactive functional groups, a hydroxyl group, an amino group, a carboxyl group, and a vinyl group are preferable.

Examples of the monomer that can be the structural unit (3) (hereinafter also referred to as “monomer (3)”) include the (meth) acrylic acid ester having the reactive functional group.
Hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate;
Amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and diethylaminopropyl (meth) acrylate;
1,4-di (meth) acryloxyethyl pyromellitic acid, 4- (meth) acryloxyethyl trimellitic acid, N- (meth) acryloyl-p-aminobenzoic acid, 2- (meth) acryloyloxybenzoic acid, Carboxyl group-containing (meth) acrylates such as N- (meth) acryloyl-5-aminosalicylic acid, acrylic acid, methacrylic acid;
Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 3,4-epoxybutyl (meth) acrylate;
Vinyl group-containing (meth) acrylates such as vinyl (meth) acrylate;
Allyl group-containing (meth) acrylates such as allyl (meth) acrylate;
Chloro group-containing (meth) acrylates such as 3-chloro-2-hydroxypropyl methacrylate, ethyl-2- (chloromethyl) acrylate, 4-chlorophenyl acrylate, methyl α-chloroacrylate;
Examples include thiol group-containing (meth) acrylates such as 2- (methylthio) ethyl methacrylate. These may be used alone or in combination of two or more.

  The content of the structural unit (3) in the polymer (A) is usually 0 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 2 parts per 100 parts by weight of the structural unit (1). ~ 20 parts by weight. When the cross-linking agent having cross-linking reactivity with respect to the functional group is used by containing the structural unit (3) in the polymer (A) in an amount within the above range, a cross-linking structure of the main agent and the cross-linking agent is formed. A release layer that can be formed satisfactorily and has excellent heat resistance, solvent resistance, substrate adhesion, and the like can be formed.

  The polymer (A) may have a side chain containing a double bond, preferably a double bond active in energy rays. By having a side chain containing an active double bond in such an energy ray, it is possible to form a crosslinked structure by irradiating the energy ray, and it is excellent in heat resistance, solvent resistance, substrate adhesion, etc. A release layer can be formed.

  For example, when the polymer (A) having a side chain containing a double bond has a hydroxyl group as a reactive functional group in the structural unit (3), the double bond is combined with an isocyanate group that is a functional group that reacts with the hydroxyl group. It can be obtained by reacting a compound having, specifically 2-isocyanatoethyl (meth) acrylate. Moreover, the polymer (A) which has a side chain containing a double bond can be obtained by copolymerizing the monomer which has a double bond in a side chain, for example, allyl (meth) acrylate etc.

  The number of double bonds active in the energy ray is desirably in the range of 1 to 50, preferably 2 to 20, per molecule of the polymer (A). When the double bond is within the above range, the crosslinking reaction by energy beam irradiation sufficiently proceeds, so that a release layer excellent in heat resistance, solvent resistance, substrate adhesion, peelability and the like can be formed. it can.

The said polymer (A) can be manufactured by well-known polymerization methods, such as emulsion polymerization and solution polymerization, using a monomer (1) and the said other monomer as needed. Examples of combinations of the monomers include, for example, combinations of monomers (1) and (2), combinations of monomers (1) and (3), monomers (1), (2) and (3 ), And the monomer (1) may be used alone. When the polymer (A) is a copolymer, it may be a random copolymer or a block copolymer.

  Further, the polymer (A) may be copolymerized with, for example, vinyl acetate, polystyrene, methacryloxypropyltrimethoxysilane, and the like in addition to the monomers as long as the object of the present invention is not impaired.

  The weight average molecular weight (Mw) of the polymer (A) used in the present invention is usually 10,000 to 2,000,000, preferably 50,000 to 1,000,000. When Mw of the polymer (A) is within the above range, the release agent composition can be applied satisfactorily, and the release performance of the release layer is also improved.

(B) Crosslinking agent The release agent composition of the present invention may contain a crosslinking agent in addition to the polymer (A). As the crosslinking agent (B) that can be used in the present invention, when the polymer (A) is composed of only a structural unit having no reactive functional group, for example, a urethane compound, a urea compound, an amide compound, an amino resin, energy Examples thereof include a linear curable compound.

  When a urethane compound is used as a crosslinking agent, for example, a crosslinked structure can be formed by adding a hydroxyl group-containing compound and an isocyanate group-containing compound to the polymer (A) and urethanizing. Similarly, when a urea compound is used as a crosslinking agent, a crosslinked structure can be formed by adding an amino group-containing compound and an isocyanate group-containing compound to form a urea, and when an amide compound is used as a crosslinking agent. A crosslinked structure can be formed by adding a carboxyl group-containing compound and an isocyanate group-containing compound to amidation.

  The hydroxyl group-containing compound is not particularly limited. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, bisphenol A, glycerin, trimethylolpropane, triethanolamine, pentaerythritol. Sorbitol, mannitol, polyvinyl alcohol, alkyd resin having a hydroxyl group at the terminal, polyethylene glycol and the like.

  Although it does not specifically limit as said amino group containing compound, For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, N, N'-diphenylethylenediamine, p-xylylenediamine etc. are mentioned.

  The carboxyl group-containing compound is not particularly limited, and examples thereof include malonic acid, succinic acid, adipic acid, azelaic acid, phthalic acid, and alkyd resin having a carboxyl group at the terminal.

  Although it does not specifically limit as said isocyanate group containing compound, For example, diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), xylene diisocyanate (XDI), naphthalene diisocyanate (NDI), trimethylolpropane (TMP) adduct TDI, TMP adduct IPDI and the like.

When using the said isocyanate group containing compound, in order to accelerate | stimulate a crosslinking reaction, you may use a catalyst. As such a catalyst, an amine catalyst or an organometallic catalyst is generally used, for example, N, N-dimethylcyclohexylamine, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, N′-tetra. Amine-based catalysts such as methylethylenediamine, bis-2-dimethylaminoether, triethylenediamine, triethanolamine;
Examples include stannous octoate, stannous oleate, dibutyltin diacetate, dibutyltin dilaurate, dimethyltin mercaptide, dimethyltin dimaleate, and organometallic catalysts such as lead octoate.

  The catalyst may be used singly or in combination of two or more, and is usually 0.001 to 5.0 parts by weight, preferably 0.001 to 100 parts by weight with respect to 100 parts by weight of the crosslinking agent (B). Used in an amount of 01 to 1 part by weight.

  When an amino resin is used as a cross-linking agent, a compound containing an amino group forms a cross-linked structure to form an amino resin, thereby forming a release layer excellent in solvent resistance, heat resistance, and substrate adhesion. it can.

  Such an amino group-containing compound is not particularly limited as long as it is an amino group-containing compound capable of forming a crosslinked structure. For example, a melamine compound, a guanamine compound, a urea compound, or the like can be used. More specifically, methylolated melamine derivatives, methylolated guanamine derivatives or methylolated urea derivatives obtained by addition reaction of formaldehyde with melamine, guanamine or urea under basic conditions include methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl Examples thereof include compounds obtained by reacting a lower alcohol such as alcohol and partially or completely etherified.

  In the release agent composition of the present invention, the amino resins may be used singly or in combination of two or more. Moreover, you may use an acidic catalyst in order to accelerate | stimulate a crosslinking reaction. Here, the acidic catalyst means a compound having an acid property among the compounds having a catalytic action. Such acidic catalysts include inorganic acids or organic acids. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, and dimethyl sulfuric acid. Examples of the organic acid include saturated monocarboxylic acids such as formic acid, acetic acid, and propionic acid; methanesulfonic acid, ethanesulfonic acid, and benzene. Examples thereof include sulfonic acids and sulfonic acids such as p-toluenesulfonic acid. In these, hydrochloric acid and p-toluenesulfonic acid are preferable.

  The acidic catalyst may be used singly or in combination of two or more, and is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts per 100 parts by weight of the amino resin. Used in parts by weight. When the amount of the acidic catalyst is within the above range, the crosslinking reaction of the amino resin proceeds sufficiently, and a good crosslinked structure can be formed.

  When an energy ray curable compound is used as a crosslinking agent, a crosslinking structure is formed by irradiating the release agent composition or the release layer with energy rays, so that the release layer has heat resistance, solvent resistance, substrate adhesion, etc. Can be improved.

Such energy ray curable compounds are not particularly limited as long as they are generally used. For example, allyl (meth) acrylate, benzyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol. Tetra (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoester (meth) acrylate, polyester type or polyether Type urethane (meth) acrylate oligomer, polyester (meth) acrylate, polyether (meth) acrylate, epoxy-modified (meth) acrylate, dipentaerythritol hexaacrylate, neopenty Such as glycol diacrylate can be used.

  In the release agent composition of the present invention, the energy ray curable compounds may be used singly or in combination of two or more. A photopolymerization initiator may be used to reduce the polymerization curing time and the amount of light irradiation.

  Examples of such a photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, 2,4 -Diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, β-chloranthraquinone, 2,2-dimethoxy-1, 2-diphenylethane-1-one, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] and the like can be mentioned.

  The photopolymerization initiator may be used singly or in combination of two or more kinds, and is 0.01 to 10 parts by weight, preferably 0.1 to 100 parts by weight of the energy ray curable compound. Used in an amount of 1 to 5 parts by weight. In addition, when an energy beam is an electron beam, it is not necessary to use the said photoinitiator.

  In the release agent composition of the present invention, the amount of the crosslinking agent (B) used varies depending on the type of the crosslinking agent used, but is usually 0.01 to 230 parts by weight with respect to 100 parts by weight of the polymer (A). It is preferably used in an amount of 1 to 100 parts by weight. By using the crosslinking agent (B) within the above range, a release layer excellent in solvent resistance, heat resistance and substrate adhesion can be formed.

  When the polymer (A) is composed only of structural units having no reactive functional group, the polymer (A) and the crosslinking agent (B) are not covalently bonded to form a crosslinked structure, but the polymer (A) And a semi-IPN structure is formed by the crosslinking agent (B). Thereby, since the freedom degree of the side chain of a polymer (A) is ensured, the peeling layer excellent in peelability, base-material adhesiveness, etc. can be formed.

Further, when the polymer (A) includes the structural unit (3) having a reactive functional group, a compound having reactivity with the functional group as the crosslinking agent (B), for example,
Isocyanate compounds such as TMP adduct TDI, TMP adduct XDI, and TMP adduct HDI;
Epoxy compounds such as N, N, N ′, N′-tetraglycidylmetaxylenediamine and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane;
Aluminum chelate compounds such as aluminum trisacetylacetonate, aluminum ethylacetoacetate diisopropylate, aluminum trisethylacetoacetate;
Titanium chelate compounds such as titanium tetraacetylacetonate, titanium acetylacetonate, titanium octylene glycolate, tetraisopropoxy titanium, tetramethoxy titanium;
By using silane compounds such as tetramethoxysilane and tetraethoxysilane; or trimethoxyaluminum, a crosslinked structure of the polymer (A) and the crosslinking agent (B) is formed. The above crosslinking agent (B) is usually used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer (A). Thereby, the peeling layer excellent in heat resistance, solvent resistance, etc. can be formed.

  The release agent composition of the present invention can be obtained by mixing or reacting the above components. Moreover, the release agent composition usually contains an organic solvent from the viewpoints of coatability and handleability. As such an organic solvent, any solvent can be used without particular limitation as long as the solubility of each component is good and the solvent does not react with each component. Examples thereof include toluene, xylene, methanol, ethanol, isobutanol, n-butanol, ethyl acetate, methyl ethyl ketone, acetone, tetrahydrofuran, isopropanol, dimethylformamide, N-methylpyrrolidone and the like.

The organic solvent may be used singly or in combination of two or more, and is used so that the resin solid content is in the range of 1 to 60% by weight, preferably 1 to 20% by weight.
The release agent composition of the present invention has other additives such as an antistatic agent, a surfactant, an antioxidant, a lubricant, a flame retardant, a colorant, a light-resistant stabilizer, as long as the object of the present invention is not impaired. It may contain a heat-resistant stabilizer.

[Peeling material]
The release material according to the present invention has a release layer made of the release material composition on a substrate. As the base material, any base material that is usually used can be used without particular limitation.
Polyethylene, polypropylene, polybutene, polybutadiene, vinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyimide, polyetherimide, polyetherketone, polyetheretherketone, ethylene / vinyl acetate copolymer, ethylene / (meth) A resin film made of a resin such as acrylic acid copolymer, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polynorbornene;
Paper such as fine paper, dust-free paper, glassine paper, clay-coated paper, resin-coated paper, laminated paper (polyethylene laminated paper, polypropylene laminated paper, etc.);
Nonwoven fabric, metal foil, etc. are mentioned.

Although the thickness of the base material varies depending on various uses and base materials, for example, when a resin film is used as the base material, it is usually 6 to 300 μm, preferably about 12 to 250 μm, and a paper base material was used. In this case, the basis weight is usually 20 to 450 g / m ² , preferably 40 to 220 g / m ² .
m is ^2.

  The release layer is formed by applying the release agent composition onto the substrate by a known method such as a gravure coating method, a roll coating method, a blade coating method, a knife coating method, a bar coating method, or a spray coating method. And can be formed by drying. The thickness of the release layer is usually 0.01 to 15 μm, preferably 0.05 to 10 μm.

The release layer formed as described above is excellent in solvent resistance, heat resistance, and substrate adhesion.
Since the release material of the present invention has a release layer excellent in solvent resistance, heat resistance, substrate adhesion, and peelability, it can be used for various applications, such as pressure-sensitive adhesive sheets, tapes, labels, etc. It can be used as a release paper in the adhesive product of No. 1, and as a process release paper used in the production of synthetic leather. In particular, since the release layer does not contain a silicone compound, the release material of the present invention can be suitably used as a release material for a pressure-sensitive adhesive sheet used when manufacturing a semiconductor device or the like.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all.

The weight average molecular weight is a polystyrene equivalent weight average molecular weight measured under the following conditions using gel permeation chromatography (GPC).
(Measurement condition)
GPC measuring device: HLC-8020 manufactured by Tosoh Corporation
GPC column (passed in the following order): Tosoh Corporation TSK guard column HXL-H
TSK gel GMHXL (× 2)
TSK gel G2000HXL
Measuring solvent: Tetrahydrofuran Measuring temperature: 40 ° C
[Example 1]
100 g of cyclohexyl acrylate, 0.5 g of azobisisobutyronitrile (AIBN), and 200 mL of toluene are added to a 1 L flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a cooling tube, and 12% at 70 ° C. under a nitrogen stream. By performing the time polymerization reaction, polycyclohexyl acrylate (PCHA) having a weight average molecular weight of 100,000 was obtained. The release agent composition 1 was obtained by diluting 100 g of the obtained PCHA with toluene so that the solid content was 10% by weight.

  The obtained release agent composition 1 was applied onto a polyethylene terephthalate (PET) film having a thickness of 38 μm using a Meyer bar so that the dry film thickness was 1 μm, and then dried at 100 ° C. for 1 minute to release the release film. (Release material) was obtained.

[Example 2]
By adding 100 g of isobornyl methacrylate, 0.37 g of AIBN, and 200 mL of toluene to a 1 L flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a cooling tube, and performing a polymerization reaction at 70 ° C. for 12 hours under a nitrogen stream. Polyisobornyl methacrylate (PIBMA) having a weight average molecular weight of 56,000 was obtained. The release agent composition 2 was obtained by diluting 100 g of the obtained PIBMA with toluene so that the solid content was 10% by weight.

  The obtained release agent composition 2 was applied onto a PET film having a thickness of 38 μm using a Mayer bar so that the dry film thickness became 1 μm, and then dried at 100 ° C. for 1 minute to obtain a release film.

[Example 3]
99 g of cyclohexyl acrylate, 1 g of 2-hydroxyethyl acrylate, 0.5 g of AIBN, and 200 mL of toluene are added to a 1 L flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a cooling tube, and polymerized at 70 ° C. for 12 hours under a nitrogen stream. By carrying out the reaction, a copolymer (PHEACHA) having a weight average molecular weight of 98,000 was obtained. 3 g of TMP adduct TDI (“Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to 100 g of the obtained PHEACHA, and diluted with toluene so that the solid content was 5% by weight to obtain a release agent composition 3. .

  The obtained release agent composition 3 was applied onto a PET film having a thickness of 38 μm using a Mayer bar so that the dry film thickness was 1 μm, and then dried at 100 ° C. for 1 minute to obtain a release film.

[Example 4]
By adding 100 g of isobornyl methacrylate, 0.37 g of AIBN, and 200 mL of toluene to a 1 L flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a cooling tube, and performing a polymerization reaction at 70 ° C. for 12 hours under a nitrogen stream. Polyisobornyl methacrylate (PIBMA) having a weight average molecular weight of 56,000 was obtained. To 100 g of the obtained PIBMA, 1 g of a commercially available amino resin (“Tesazine 3103-60” manufactured by Hitachi Chemical Polymer Co., Ltd.) and 0.03 g of p-toluenesulfonic acid are added, and toluene is added so that the solid content becomes 10% by weight. To obtain a release agent composition 4.

  The obtained release agent composition 4 was applied onto a PET film having a thickness of 38 μm using a Meyer bar so that the dry film thickness became 1 μm, and then dried at 140 ° C. for 1 minute to obtain a release film.

[Example 5]
90 g of cyclohexyl acrylate, 10 g of 2- (perfluorooctyl) ethyl acrylate, 0.45 g of AIBN, and 200 mL of toluene were added to a 1 L flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a cooling tube, and 70 ° C. under a nitrogen stream. For 12 hours to obtain a copolymer (PF8CHA) of cyclohexyl acrylate having a weight average molecular weight of 140,000 and 2- (perfluorooctyl) ethyl acrylate. 100 g of the obtained PF8CHA was diluted with toluene so that the solid content was 10% by weight to obtain a release agent composition 5.

  The obtained release agent composition 5 was applied on a PET film having a thickness of 38 μm using a Mayer bar so that the dry film thickness was 1 μm, and then dried at 100 ° C. for 1 minute to obtain a release film.

[Comparative Example 1]
By adding 100 g of stearyl acrylate, 0.5 g of AIBN, and 200 mL of toluene to a 1 L flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a cooling tube, and performing a polymerization reaction at 70 ° C. for 12 hours under a nitrogen stream, Polystearyl acrylate (PSA) having an average molecular weight of 59,000 was obtained. The release agent composition 6 was obtained by diluting 100 g of the obtained PSA with toluene so that the solid content was 10% by weight.

  The obtained release agent composition 6 was applied onto a PET film having a thickness of 38 μm using a Mayer bar so that the dry film thickness was 1 μm, and then dried at 100 ° C. for 1 minute to obtain a release film.

[Comparative Example 2]
By adding 100 g of isooctyl acrylate, 0.45 g of AIBN, and 200 mL of toluene to a 1 L flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a cooling tube, and performing a polymerization reaction at 70 ° C. for 12 hours under a nitrogen stream. Polyisooctyl acrylate (POA) having a weight average molecular weight of 86,000 was obtained. The release agent composition 7 was obtained by diluting 100 g of the obtained POA with toluene so that the solid content was 10% by weight.

  The obtained release agent composition 7 was applied onto a PET film having a thickness of 38 μm using a Meyer bar so that the dry film thickness became 1 μm, and then dried at 100 ° C. for 1 minute to obtain a release film.

<Evaluation>
The following evaluation was performed about the peeling film produced using the polymer synthesize | combined in the said Examples 1-5 and Comparative Examples 1-2, and the releasing agent composition containing this polymer. The results are shown in Table 1.

(Solubility)
3 g of the obtained polymer was dissolved in 10 mL of toluene at room temperature, and the transparency was confirmed visually. A transparent solution was designated as “◯”, and a cloudy product was designated as “X”.

(Base material adhesion)
According to a cross cut test (JIS K-5400), a cross cut was made in the release layer of the obtained release film, and a silicone adhesive tape (“C-206” manufactured by Lintec Corporation) was applied and peeled off. Sometimes the number of eyes remaining on the substrate was evaluated.

(Peelability)
On the obtained release film, an adhesive (“BPS-5127” manufactured by Toyo Ink Manufacturing Co., Ltd.) was applied to a thickness of 50 μm using a test coater and dried at 100 ° C. for 2 minutes. A 50 μm thick PET film was laminated, and the peel force was measured according to JIS Z0237.

(Heat-resistant)
On the obtained release film, an adhesive (“BPS-5127” manufactured by Toyo Ink Manufacturing Co., Ltd.) was applied to a thickness of 50 μm using a test coater and dried at 100 ° C. for 2 minutes. A 50 μm thick PET film was laminated. The pressure-sensitive adhesive film was allowed to stand for 3 days under conditions of 70 ° C. and 100 g / cm ² under pressure, and then peel strength was measured according to JIS Z0237.

  As shown in Table 1, polymers having alicyclic groups (Examples 1 to 5) have high solubility in coating solvents, and are formed by release agent compositions (Examples 1 to 5) containing the polymer. It was confirmed that the release layer was superior in substrate adhesion as compared with Comparative Examples 1 and 2, and had little change in peel force before and after the heat resistance test, and was excellent in heat resistance.

Claims (4)

A release agent composition for forming a release layer of a release material for protecting an adhesive layer of an adhesive sheet,
100 parts by weight of a structural unit represented by the following general formula (1):
0 to 100 parts by weight of a structural unit represented by the following general formula (2);
A release agent composition comprising a poly (meth) acrylate (A) composed of 0 to 30 parts by weight of a structural unit derived from a (meth) acrylate having a reactive functional group.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alicyclic group having 5 to 18 carbon atoms, and the alicyclic group may contain an oxygen atom or a nitrogen atom.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ³ represents an alkyl group having 1 to 28 carbon atoms or an aromatic group, and the alkyl group may contain a fluorine atom, an oxygen atom or a nitrogen atom. Good.) The release agent composition according to claim 1 , wherein the poly (meth) acrylic acid ester (A) does not have a reactive functional group. On at least one side of the substrate, the release material characterized by having a release layer comprising a release agent composition according to any one of claims 1-2. A pressure-sensitive adhesive sheet comprising the release material according to claim 3 and an adhesive layer, wherein the release layer of the release material is laminated on the adhesive layer.