Composition

Abstract

To provide a composition that is free of contamination, has excellent smoothness and curability, and stably gives releasability and light-peelability, and a cured product of the composition having releasability and light-peelability, and a release sheet.SOLUTION: A composition contains a polyol (A) containing, in one molecule, a sugar residue with 6 or more carbon atoms, and having an alkylene oxide residue and four or more hydroxy groups, and a melamine crosslinker (F).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a composition containing a polyol having a sugar residue with six or more carbon atoms in one molecule, an alkylene oxide residue, and four or more hydroxyl groups, and a melamine crosslinker, and a cured product containing a reaction product of the composition. [Background technology]

[0002] Compositions that impart releasability or easy peelability are used in a variety of applications requiring easy peelability, such as release materials for protecting adhesive tapes and the like, and pressure-sensitive adhesives for protective films that protect various adherends.

[0003] In particular, in the field of electronic devices, release sheets having a release layer obtained using a release agent composition are widely used in the manufacturing process of semiconductor devices and ceramic green sheets, and the composition is required to have not only light releasability but also smoothness with few pinholes and thickness unevenness and not contaminate the adherend.

[0004] In Patent Document 1, a release sheet is produced by applying and curing a composition containing a (meth)acrylate component and a modified silicone oil modified with a (meth)acryloyl group and / or a vinyl group onto a substrate, thereby forming a layer containing a cured product of the (meth)acrylate component and a layer containing a silicone component as a release material layer on the substrate. However, because the composition contains a silicone component as a component that forms the release layer, the composition cannot be expected to have stain resistance due to the transfer of silicone, and further, because the silicone lowers the surface energy, the composition cannot be expected to achieve both wettability and pinhole-free smoothness.

[0005] That is, there has been a demand for a composition that can stably impart mold releasability and easy peelability, and that is excellent in wettability, smoothness, and stain resistance, without relying on silicone components. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 5423975 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention provides a composition that is stain-free, has excellent smoothness, and has good curability, and can stably impart releasability and easy releasability, as well as a cured product and release sheet that have releasability and easy releasability obtained by curing the composition. [Means for solving the problem]

[0008] The embodiments of the present invention are as follows [1] to

[11] . [1] A composition (G) comprising a polyol (A) containing a sugar residue having 6 or more carbon atoms in one molecule, an alkylene oxide residue, and 4 or more hydroxyl groups, and a melamine crosslinker (F). [2] The composition (G) according to [1], wherein the melamine crosslinking agent (F) comprises a methylol melamine derivative or an alkylated melamine derivative thereof. [3] The composition (G) according to [1] or [2], wherein the melamine crosslinking agent (F) has one or more imino groups and is self-condensing. [4] Composition (G) according to any one of [1] to [3], further comprising a polyalkylene oxide (B) having 2 to 3 hydroxyl groups in one molecule and having a number average molecular weight of 1,500 or more. [5] Composition (G) according to any one of [1] to [4], further comprising a polyalkylene oxide (C) having one hydroxyl group and an ethylene oxide residue in one molecule and having a number average molecular weight in the range of 300 or more but less than 1,500. [6] The composition (G) according to any one of [1] to [5], further comprising a urethane prepolymer (E) which is a reaction product of the polyol (A) and an isocyanate compound (D). [7] The urethane prepolymer (E) has a weight average molecular weight of 1,000 or more and at least one hydroxyl group in one molecule, The composition (G) according to [6], wherein the weight ratio of the urethane prepolymer (E) to the melamine crosslinking agent (F) is in the range of 30 / 70 to 95 / 5. [8] A composition solution (H) comprising the composition (G) according to any one of [1] to [7] and an organic solvent. [9] A cured product (I) comprising a reaction product of the composition (G) according to any one of [1] to [7].

[10] A release coating film comprising the cured product (I) according to [9].

[11] A release sheet characterized by having a release material layer made of the release material coating film described in

[10] on at least one surface of a substrate. [Effects of the Invention]

[0009] The composition of the present invention is a composition that can stably impart mold releasability and easy peelability without containing a silicone component, and is excellent in curability and smoothness.

[0010] Furthermore, by forming a layer containing a cured product obtained using the composition of the present invention on a substrate, the composition can be suitably used in a wide range of applications, such as release materials and lightly releasable films. DETAILED DESCRIPTION OF THE INVENTION

[0011] Exemplary embodiments for carrying out the present invention are described in detail below.

[0012] The composition (G) according to one embodiment of the present invention contains a polyol (A) containing a sugar residue having 6 or more carbon atoms in one molecule, an alkylene oxide residue and 4 or more hydroxyl groups, and a melamine crosslinking agent (F). <Polyol (A)> The polyol (A) is not particularly limited as long as it contains a sugar residue having 6 or more carbon atoms in one molecule, an alkylene oxide residue, and four or more hydroxyl groups, and may be one in which one type of alkylene oxide is linked in a chain to a sugar having 6 or more carbon atoms, or one in which multiple alkylene oxides are linked in a chain or randomly to a sugar having 6 or more carbon atoms.

[0013] The alkylene oxide residue is not particularly limited, and examples thereof include alkylene oxide residues having 2 to 20 carbon atoms. Specific examples thereof include ethylene oxide residue, propylene oxide residue, 1,2-butylene oxide residue, 2,3-butylene oxide residue, isobutylene oxide residue, butadiene monoxide residue, pentene oxide residue, styrene oxide residue, and cyclohexene oxide residue.

[0014] The alkylene oxide residue may contain only a single alkylene oxide residue or may contain two or more types of alkylene oxide residues. When two or more types of alkylene oxide residues are contained, for example, one type of alkylene oxide residue may be linked in a chain to another alkylene oxide residue, or two or more types of alkylene oxide residues may be linked randomly.

[0015] Among these, alkylene oxides are preferred because they are industrially readily available, can be synthesized easily, and tend to have good moldability: those in which only propylene oxide is linked in a chain to a sugar having 6 or more carbon atoms, those in which only ethylene oxide is linked in a chain to a sugar having 6 or more carbon atoms, and those in which propylene oxide and ethylene oxide are linked in a chain or randomly to a sugar having 6 or more carbon atoms; and most preferred is those in which only propylene oxide residues are linked in a chain to a sugar having 6 or more carbon atoms, because these do not solidify easily even at low temperatures and can be used over a wide range of temperature conditions.

[0016] Polyol (A) exhibits high releasability and easy peelability by containing a rigid sugar residue having 6 or more carbon atoms, and exhibits wettability and pinhole-free smoothness by containing a relatively flexible alkylene oxide residue. Therefore, if it does not contain a sugar residue, it is difficult to use because it does not provide enough releasability or easy peelability, and if it does not contain an alkylene oxide residue, it lacks flexibility and the resulting coating film tends to have a brittle structure, which leads to poor moldability and poor wettability of the resulting cured product, making it difficult to use.

[0017] The polyol (A) has four or more hydroxyl groups per molecule. The number of hydroxyl groups in the polyol (A) is not particularly limited as long as it has an average of four or more hydroxyl groups per molecule. However, the number of hydroxyl groups per molecule is preferably 4 to 12, more preferably 5 to 8, because this makes it easier to obtain a uniform crosslinked structure by the reaction of the polyol (A) with the melamine crosslinking agent (D) and to achieve both good releasability and brittleness of the resin. If the polyol (A) contains fewer than four hydroxyl groups, the degree of crosslinking of the resulting cured product decreases, making it difficult to stably impart good releasability and easy peelability.

[0018] The number average molecular weight of the polyol (A) is not particularly limited and may be appropriately selected depending on the application, but is preferably from 100 to less than 3000, more preferably from 300 to less than 2000 because this facilitates the development of significantly high releasability, and most preferably from 500 to less than 1500. When the number average molecular weight of the polyol (A) is less than 3000, it is likely to contain a large number of sugar residues having 6 or more carbon atoms, which is preferable because this facilitates the improvement of releasability.

[0019] The number average molecular weight of the polyol (A) can be calculated from the hydroxyl value of the polyol (A) calculated by the method described in JIS K-1557-1 and the number of hydroxyl groups in one molecule of the polyol (A). The hydroxyl value (mgKOH / g) of the polyol (A) is not particularly limited, but is preferably more than 70 and not more than 2000, more preferably more than 180 and not more than 1000, and most preferably more than 250 and not more than 700.

[0020] The viscosity of the polyol (A) at 25°C is not particularly limited and may be appropriately selected depending on the application, but is preferably from 1,000 mPa·s to 100,000 mPa·s, and more preferably from 5,000 mPa·s to 50,000 mPa·s. A viscosity of from 1,000 mPa·s to 100,000 mPa·s is preferred because it results in a high content of sugar residues having 6 or more carbon atoms and tends to improve mold releasability.

[0021] The polyol (A) has a sugar residue having 6 or more carbon atoms per molecule. The structure of the sugar residue in the polyol (A) is not particularly limited as long as it has a sugar residue having 6 or more carbon atoms per molecule, but the sugar residue is preferably a sugar residue having 6 to 20 carbon atoms per molecule, and more preferably a sugar residue having 6 to 12 carbon atoms per molecule. Examples of such sugar residues include maltitol residue, maltose residue, glucose residue, fructose residue, sucrose residue, and sorbitol residue. Sucrose residue or sorbitol residue is preferred because the raw materials are easily available and they tend to exhibit good curing properties and releasability. Of these, the inclusion of a sucrose residue is most preferred because it has a cyclic structure and tends to exhibit good releasability.

[0022] The polyol (A) is generally obtained by ring-opening polymerization of alkylene oxide using a sugar having 6 or more carbon atoms, such as sucrose or sorbitol, as an initiator. However, it may also be synthesized by using a low-viscosity active hydrogen compound that does not contain a sugar residue having 6 or more carbon atoms, such as diethylenetriamine, triethanolamine, diethylene glycol, glycerin, or propylene glycol, in combination with the initiator, and may contain a component having the above residue.

[0023] For example, sorbitol normally has 6 hydroxyl groups, and sucrose normally has 8 hydroxyl groups, but the number of hydroxyl groups can be reduced by using an initiator that does not contain a sucrose or sorbitol residue, or by capping the ends.

[0024] Commercially available polyalkylene oxides containing sucrose residues include Huntsman's JEFFOLS A-499 (nominal functionality 4.3, hydroxyl value 495), JEFFOL SD-361 (nominal functionality 4.4, hydroxyl value 360), and JEFFOLS G-522 (nominal functionality 5.0, hydroxyl value 520), and Toho Chemical Industry's Toho Polyol O-850 (nominal functionality 8, hydroxyl value 380). Examples of polyalkylene oxides containing sorbitol residues include Huntsman's JEFFOLS-490 (nominal functionality 4.7, hydroxyl value 490), and these can be suitably used. <Melamine crosslinker (F)> The melamine crosslinking agent (F) is not particularly limited as long as it contains a melamine structure, and examples thereof include a structure represented by the following general formula (1).

[0025] [ka]

[0026] [In general formula (1), R1 to R6 each independently represent a hydrogen atom or an alkyl group, an aryl group, an alkenyl group, a benzyl group, a hydroxy group, an alkanoyl group, an alkylol group, or an alkoxyalkyl group, which may be the same or different, and may be partially or completely bonded to form a cyclic structure or a condensed structure.] The alkyl group of R1 to R6 is not particularly limited, but is preferably an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, and a hexyl group.

[0027] The aryl group of R1 to R6 is not particularly limited, but examples thereof include a phenyl group, a pyridyl group, a naphthyl group, a biphenyl group, a phenoxy group, and a toluenesulfonyl group.

[0028] The alkylol groups of R1 to R6 are not particularly limited, but alkylol groups having 1 to 12 carbon atoms are preferred, and examples thereof include methylol, butyrol, and ethylol groups, which can be suitably used.

[0029] The alkoxyalkyl group of R1 to R6 is not particularly limited, but preferably includes an alkyl group having 1 to 12 carbon atoms and an alkoxyl group having 1 to 12 carbon atoms, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a pentyloxymethyl group, a methoxybutyl group, an ethoxybutyl group, a propoxybutyl group, and a butoxybutyl group, and these can be suitably used.

[0030] The structure in which some or all of R1 to R6 are bonded and condensed is not particularly limited, but is preferably a structure in which some or all of a hydrogen atom (imino group), an alkylol group, or an alkoxyalkyl group are bonded and condensed. For example, condensed structures containing an alkyl group (-(CH2)n-) or an alkyl ether group (-(CH2)nO-(CH2)n-), which are condensed groups with these same or different groups, can be preferably used.

[0031] Among these, R1 to R6 in general formula (1) are preferably any of a hydrogen atom, an alkylol group, an alkoxyalkyl group, or a structure containing a condensed group thereof, because these are commercially available and tend to exhibit good curability stably. Examples of such melamine crosslinking agents (F) include melamine, methylolated melamine derivatives obtained by condensing melamine with formaldehyde and methylolating some or all of the methylol groups, alkylated melamine derivatives obtained by alkylating some or all of the methylol groups of methylolated melamine, etc. The melamine crosslinking agent (F) may be either a mononuclear compound or a condensation product of a polynuclear compound having two or more nuclei, or a mixture thereof may be used.

[0032] Examples of the di- or higher polynuclear melamine crosslinking agent (F) include structures containing two or more melamine structures, and are not particularly limited thereto. For example, a structure represented by general formula (2) condensed with formaldehyde can be used.

[0033] [ka]

[0034] [In general formula (1), R to R 14are each independently a hydrogen atom or an alkyl group, an aryl group, an alkenyl group, a benzyl group, a hydroxy group, an alkanoyl group, an alkylol group, or an alkoxyalkyl group, which may be the same or different, and may be bonded in part or in whole to form a cyclic structure. When n is 2 or more and there are multiple R6 to R9, they are each independently the same or different, and n is an integer of 0 to 100. R1~R 14 The substituents of the aryl group include the substituents and structures exemplified for the mononuclear compound, and the preferred structures are also the same.

[0035] The inclusion of melamine crosslinker (F) allows the introduction of a rigid melamine structure, which results in high releasability and easy peelability. Therefore, if melamine crosslinker (F) is not included, the stable high releasability and easy peelability are not sufficiently achieved, making it difficult to use.

[0036] Among these, the melamine crosslinking agent (F) is preferably a methylolated melamine derivative or an alkylated melamine derivative thereof, because a denser crosslinked structure can be formed by a crosslinking reaction with the polyol (A), which facilitates the development of high releasability and easy peelability. Examples of such melamine crosslinking agents (F) include imino group-containing methylolated melamines in which some of the amino groups of melamine are methylolated, imino group-containing alkylated melamines in which the methylol groups of imino group-containing methylolated melamines are alkylated, fully alkylated melamines in which the methylol groups are completely alkylated, methylol group-containing alkylated melamines in which some of the methylol groups are alkylated, and mixtures thereof, and these can be suitably used.

[0037] More preferably, the melamine crosslinking agent (F) contains an imino group (—NR—H) and has self-condensation properties, because it has high self-condensation properties, improves the degree of crosslinking, and is more likely to further exhibit high releasability and easy peelability, and the amount of free formalin is small, which tends to improve stain resistance and workability. Examples of such melamine crosslinking agents (F) include imino group-containing methylol melamine, imino group-containing alkylated melamine, and mixtures thereof, which can be suitably used, and imino group-containing alkylated melamine is most preferred.

[0038] When using an alkylated melamine derivative in which some or all of the methylol groups of methylolated melamine are alkylated as the melamine crosslinking agent (F), the alkyl group preferably contains one of a methyl group, an ethyl group, a propyl group, or a butyl group, because these groups are versatile, readily available, and readily exhibit releasability and by-product removal. Among these, a methyl group, a combination of a methyl group and a normal butyl group, or a combination of a methyl group and an ethyl group is preferred, because these groups have good flow properties and tend to produce smooth coating films even in thin films upon drying and curing. Most preferred is an alkylated melamine derivative consisting solely of a methyl group.

[0039] The melamine crosslinking agent (F) is not particularly limited, but preferably contains an alkoxy group, a methylol group, an imino group, or the like as a reactive group. Among these, the crosslinking degree of the resulting cured product tends to be high, and the easy peelability and releasability tend to be improved. Therefore, it is preferable for one molecule to contain three or more reactive groups, more preferably four or more, and most preferably six or more. Among these, the number of functional groups of the mononuclear units in the melamine crosslinking agent (F) is preferably in the range of 3 to 20, more preferably in the range of 4 to 6, in order to easily achieve both wettability and releasability of the coating film.

[0040] The melamine crosslinked material (F) may be used alone or in combination of two or more kinds.

[0041] When the melamine crosslinking agent (F) contains a mononuclear compound and a polynuclear compound, the ratio of mononuclear compounds in the melamine derivative is not particularly limited, but if it is too low, the number of reactive groups in one molecule will be too high, which may result in poor wettability and reduced smoothness in the resulting coating film, so it is preferably 10% or more, more preferably in the range of 30% to 70%, and most preferably in the range of 40% to 55%, so that the coating film can easily achieve both good wettability and releasability.

[0042] The weight-average molecular weight of the melamine crosslinking agent (F) is not particularly limited, but in order to achieve good handleability and compatibility with the polyol (A) and to easily achieve both wettability and releasability of the coating film, it is preferably from 100 to less than 50,000, more preferably from 150 to less than 20,000, and most preferably from 200 to less than 10,000. The weight-average molecular weight of the melamine crosslinking agent (F) can be measured by a conventional method using gel permeation chromatography (GPC).

[0043] The melamine crosslinking agent (F) may contain a diluent solvent if necessary, and isobutanol, isopropanol, 1-butanol, etc. are preferably used, although they are not particularly limited. <Composition (G)> The composition (G) of one embodiment of the present invention is not particularly limited as long as it contains the above-mentioned polyol (A) and melamine crosslinking agent (F), and may contain other components. In particular, it is preferable that the composition (G) contains, in addition to the essential components of polyol (A) and melamine crosslinking agent (F), a polyalkylene oxide (B) having 2 to 3 hydroxyl groups per molecule and a number average molecular weight of 1,500 or more, because this improves the coatability of the composition (G), makes it easier to suppress shrinkage during curing, and also makes it easier to achieve excellent wettability and coating film smoothness.

[0044] The number average molecular weight of the polyalkylene oxide (B) is preferably 1,500 or more and less than 30,000, more preferably 2,000 or more and less than 13,000, and most preferably 3,000 or more and less than 10,000, as this tends to further improve the smoothness of the coating film. The number average molecular weight of the polyalkylene oxide (B) can be calculated from the hydroxyl value of the polyalkylene oxide (B) calculated by the method described in JIS K-1557-1 and the number of hydroxyl groups in one molecule of the polyalkylene oxide (B). The hydroxyl value (mgKOH / g) of the polyalkylene oxide (B) is not particularly limited, but is preferably 3 or more and 250 or less, more preferably 5 or more and 180 or less, and most preferably 8 or more and 70 or less.

[0045] The polyalkylene oxide (B) preferably contains an alkylene oxide residue having 3 or more carbon atoms. The alkylene oxide residue having 3 or more carbon atoms is not particularly limited, and examples thereof include alkylene oxide residues having 3 to 20 carbon atoms. Specific examples include propylene oxide residue, 1,2-butylene oxide residue, 2,3-butylene oxide residue, isobutylene oxide residue, butadiene monoxide residue, pentene oxide residue, styrene oxide residue, and cyclohexene oxide residue. Among these alkylene oxide residues, propylene oxide residue is preferred because the raw materials for obtaining the polyalkylene oxide (B) are easily available and the resulting polyalkylene oxide (B) has high industrial value.

[0046] Furthermore, the polyalkylene oxide (B) may contain only a single alkylene oxide residue as the alkylene oxide residue having 3 or more carbon atoms, or may contain two or more types of alkylene oxide residues. When two or more types of alkylene oxide residues are contained, for example, one type of alkylene oxide residue may be linked in a chain to another alkylene oxide residue, or two or more types of alkylene oxide residues may be linked randomly. Furthermore, the polyalkylene oxide (B) preferably contains an alkylene oxide residue having 3 or more carbon atoms, and may additionally contain an ethylene oxide residue having 2 carbon atoms.

[0047] Furthermore, the polyalkylene oxide (B) has 2 to 3 hydroxyl groups per molecule. When the number of hydroxyl groups per molecule of the polyalkylene oxide (B) is 2 to 3, the resulting coating film tends to have large tensile elongation at break and large tensile strength at break, and the wettability and smoothness of the coating film tend to be excellent, while the coating film is less susceptible to cracking.

[0048] The degree of unsaturation of the polyalkylene oxide (B) is not particularly limited, but is preferably 0.010 meq / g or less, more preferably 0.007 meq / g or less, and most preferably 0.004 meq / g or less, because this reduces the amount of monool, making it easier to reduce the contamination of the coating film and to improve the curability and releasability.

[0049] When such a polyalkylene oxide (B) having a low degree of unsaturation is used, it is obtained by ring-opening polymerization of an alkylene oxide using an active hydrogen-containing compound as an initiator in the presence of an alkylene oxide polymerization catalyst containing a phosphazene compound and a Lewis acid. Therefore, the polyalkylene oxide (B) has an alkylene oxide residue.

[0050] Here, the "degree of unsaturation (meq / g)" of the polyalkylene oxide (B) refers to the amount of unsaturated groups contained in 1 g of the polyalkylene oxide, and corresponds to the number of unsaturated monools contained in the polyalkylene oxide. That is, the higher the degree of unsaturation, the more unsaturated monools there are, and the lower the degree of unsaturation, the fewer unsaturated monools there are.

[0051] In this embodiment, the degree of unsaturation of the polyalkylene oxide was measured in accordance with the NMR method described in Kobunshi Ronbunshu 1993, 50, 2, 121-126. In this embodiment, since the polyalkylene oxide having a small amount of unsaturated monool is the object of measurement, the number of scans in the NMR measurement is 500 or more to improve the measurement accuracy.

[0052] When polyalkylene oxide (B) is used, the mixing ratio of polyol (A) to polyalkylene oxide (B) in composition (G) is not particularly limited, but is preferably in the range of 5 / 95 to 95 / 5 in mass ratio (polyol (A) / polyalkylene oxide (B)), more preferably in the range of 10 / 90 to 70 / 30, and most preferably in the range of 15 / 85 to 50 / 50, since this makes it easy to significantly suppress deterioration of smoothness due to cure shrinkage and the like while maintaining mold releasability and easy peelability.

[0053] Composition (G) is likely to have excellent coatability and further tends to have excellent smoothness and releasability of the coating film. Therefore, in addition to the essential components polyol (A) and melamine crosslinker (F), it is preferred that composition (G) contain polyalkylene oxide (C) having one hydroxyl group and one ethylene oxide residue per molecule and having a number average molecular weight in the range of 300 or more and less than 1,500.

[0054] The polyalkylene oxide (C) contains one hydroxyl group and one ethylene oxide residue per molecule, and is preferably at least one selected from the group consisting of polyoxyalkylene glycol monoalkyl ethers, polyoxyalkylene glycol monoalkenyl ethers, and polyoxyalkylene glycol monophenyl ethers, as this provides particularly excellent coatability when the composition (G) is applied using a coater or the like.

[0055] The polyoxyalkylene glycol monoalkyl ether is not particularly limited, and examples thereof that can be suitably used include polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monobutyl ether, polyoxy(ethylene-propylene) glycol monomethyl ether, polyoxy(ethylene-propylene) glycol monobutyl ether, polyoxyethylene glycol monolaurate, polyoxyethylene glycol monolaurylamine, etc. Also usable are polyoxyalkylene glycol monoalkyl ether salts having an amino group or inorganic salts such as sulfates, such as polyoxyethylene lauryl ether triethanolamine sulfate.

[0056] Among these, in order to achieve excellent coatability and smoothness when applying composition (G), it is preferred that the content of ethylene oxide residues is 50% or more and that the composition contains one or more of polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monobutyl ether, polyoxy(ethylene-propylene) glycol monomethyl ether, and polyoxy(ethylene-propylene) glycol monobutyl ether.

[0057] Here, the number average molecular weight of the polyalkylene oxide (C) is 300 or more and less than 1,500, preferably 350 or more and less than 1,200, and most preferably 500 or more and less than 900.

[0058] The polyalkylene oxide (C) is unlikely to become unstable in composition due to volatilization, is unlikely to crystallize even at low temperatures, has excellent handleability, and when applied using a coating machine or the like, easily gives a coating film with a uniform thickness, a smooth surface, and high transparency. The number average molecular weight of the polyalkylene oxide (C) is preferably 300 or more and less than 1,500.

[0059] The number average molecular weight of the polyalkylene oxide (C) can be calculated from the hydroxyl value of the polyalkylene oxide (C) calculated by the method described in JIS K-1557-1 and the number of hydroxyl groups in one molecule of the polyalkylene oxide (C).

[0060] When polyalkylene oxide (C) is used, the mixing ratio of polyol (A) to polyalkylene oxide (C) in composition (G) is not particularly limited, but is preferably in the range of 85 / 15 to 99.9 / 0.1 in mass ratio (polyol (A) / polyalkylene oxide (C)), more preferably in the range of 90 / 10 to 99.7 / 0.3, and most preferably in the range of 95 / 5 to 99.5 / 0.5, since this tends to provide excellent releasability and easy peelability while maintaining low contamination.

[0061] The mixing ratio of the melamine crosslinking agent (F) to the total amount of the polyol (A) and the polyalkylene oxides (B) and (C) contained as needed in the composition (G) is not particularly limited, but a mass ratio ((polyol (A) + polyalkylene oxide (B) + polyalkylene oxide (C)) / melamine crosslinking agent (F)) of 30 / 70 to 90 / 10 is preferred because it provides good flowability, easily suppresses cure shrinkage, and is easy to achieve excellent releasability and light peelability. Of these, a range of 50 / 50 to 85 / 15 is preferred, and a range of 60 / 40 to 80 / 20 is most preferred because it provides significantly excellent releasability.

[0062] Composition (G) may contain, in addition to polyol (A) and, if necessary, polyalkylene oxide (B) and polyalkylene oxide (C), other polyols. The other polyols are not particularly limited, but are compounds having one or more hydroxyl groups, and specific examples thereof include polyoxytetramethylene glycol, polycarbonate polyol, polyester polyol, Mannich polyol, polyolefin polyol, acrylic polyol, and low-molecular-weight polyols such as butanediol and 3-methyl-1,5-pentanediol.

[0063] The composition (G) may contain, as necessary, a catalyst, an antioxidant, a light stabilizer, a leveling agent, a plasticizer, a release agent, and other additives.

[0064] The content of additives in composition (G) is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less. When a compound containing a silicon component is used, it is prone to contamination and deterioration of smoothness, so the content is preferably 0.5% by mass or less, and most preferably not used.

[0065] As the catalyst, an acid catalyst is preferably used to enhance the self-condensation and curing properties of the melamine crosslinking agent (F), and aromatic sulfonic acid derivatives and phosphoric acid derivatives are suitable for use as such acid catalysts. When forming a urethane prepolymer, tertiary amine compounds, organometallic compounds, etc., can be used, and examples of suitable compounds that can be used include triethylenediamine, diazabicycloundecene (also known as DBU), dibutyltin dilaurate (also known as DBTDL), dioctyltin dilaurate (also known as DOTDL), tin 2-ethylhexanoate, and iron trisacetylacetonate.

[0066] Examples of the release agent include fluorine-based compounds, silicone-based compounds, surfactant-based compounds, wax-based compounds, etc., which can be used as long as the staining resistance and smoothness are within acceptable ranges. Among them, the above-exemplified compounds having a hydroxyl group are preferred because they are reactive with the melamine crosslinking agent (F), have low staining resistance, and have a high release property-imparting effect. Examples include fluorine-containing polyols and silicone-containing monools having hydroxyl groups at the terminals or inside the molecule, surfactant-based compounds and wax-based compounds containing hydroxyl groups, etc. However, when a release agent containing a silicone component is used, even if it has a hydroxyl group, even a small amount of residual hydroxyl group can easily cause staining and deteriorate smoothness, so surfactant-based compounds and wax-based compounds containing a hydroxyl group and a long-chain alkyl group can be most preferably used.

[0067] The preparation of composition (G) is not particularly limited as long as it is a method capable of uniformly dispersing the raw materials contained in composition (G), and various conventionally known stirring methods can be used, such as a method of stirring using a stirrer. Examples of stirrers include general-purpose stirrers, planetary mixers, planetary mixers, kneaders, mixers, laboplastomills, and planetary mixers. Among these, when all the raw materials are liquid at the stirring temperature (including solutions and masterbatches), planetary mixers, planetary mixers, dispersers, and planetary mixers are preferably used.

[0068] The viscosity of composition (G) at 25°C is not particularly limited, but is usually from 0.1 mPa·s to 100,000 mPa·s, preferably from 1 mPa·s to 10,000 mPa·s, and more preferably from 10 mPa·s to 1,000 mPa·s. When the viscosity of composition (G) at 25°C is within this range, stirring and handling of the composition are facilitated, which is preferable when stirring with various stirrers to prepare composition (G) or when stirring as a preliminary step before applying composition (G) with a coating machine or the like. <Urethane prepolymer (E)> The composition (G) which is one embodiment of the present invention may contain a urethane prepolymer (E) which is a reaction product of a polyol (A) and an isocyanate compound (D).

[0069] The urethane prepolymer (E) is preferably formed by reacting the polyol (A) in the composition (G) with the isocyanate compound (D).

[0070] In addition, when the composition (G) contains the polyalkylene oxide (B) and the polyalkylene oxide (C), the urethane prepolymer (E) may be formed by using the polyalkylene oxide (B) and part or all of the polyalkylene oxide (C) in combination.

[0071] That is, when composition (G) contains urethane prepolymer (E), it may contain one or more of the following: a urethane prepolymer of the polyol (A) and an isocyanate compound (D), a urethane prepolymer of the polyol (A), a polyalkylene oxide (B), and an isocyanate compound (D), a urethane prepolymer of the polyol (A), a polyalkylene oxide (C), and an isocyanate compound (D), and a urethane prepolymer of the polyol (A), a polyalkylene oxide (B), and a urethane prepolymer of the polyol (A), a polyalkylene oxide (C), and an isocyanate compound (D). In addition to the polyalkylene oxide (B) or polyalkylene oxide (C), other polyols may be used in combination to form the urethane prepolymer (E).

[0072] The isocyanate compound (D) used to form the urethane prepolymer (E) is not particularly limited as long as the average functionality of the isocyanate group is 2.0 or more. Examples of the isocyanate compound (D) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexyl methyl acrylate, methyl acrylate, methyl acrylate, methyl acrylate ... Examples of the isocyanate include xylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, modified isocyanates obtained by reacting these with polyalkylene oxides, and mixtures of two or more of these. Further examples include modified products of these isocyanates containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, an isocyanurate group, an amide group, an imide group, a uretonimine group, a uretdione group, or an oxazolidone group, and condensates such as polymethylene polyphenylene polyisocyanate (polymeric MDI).

[0073] Among these, aliphatic isocyanates, alicyclic isocyanates, or modified products thereof are preferred because they facilitate the production of highly transparent coating films with little coloration. 1,6-hexamethylene diisocyanate, isophorone diisocyanate, aliphatic isocyanate-containing prepolymers, alicyclic isocyanate-containing prepolymers, or modified products of these isocyanates containing urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, isocyanurate groups, amide groups, imide groups, uretonimine groups, uretdione groups, or oxazolidone groups are more preferred. These isocyanates may be used alone or in combination of two or more.

[0074] The urethane prepolymer (E) has a weight-average molecular weight of 1000 or more and at least one hydroxyl group per molecule, and the weight ratio of the urethane prepolymer (E) to the melamine crosslinking agent (F) is preferably in the range of 30 / 70 to 95 / 5. In particular, the weight ratio of the urethane prepolymer (E) to the melamine crosslinking agent (F) is preferably in the range of 50 / 50 to 90 / 10, and most preferably in the range of 60 / 40 to 85 / 15, because this tends to result in significantly excellent mold releasability.

[0075] When forming the urethane prepolymer (E), the weight average molecular weight of the urethane prepolymer (E) is preferably 1000 or more, and in particular, it is preferably in the range of 2000 or more but less than 1,000,000, and most preferably in the range of 3000 or more but less than 500,000, as this tends to provide a moderate viscosity and excellent moldability.

[0076] The total amount of hydroxyl groups (M) derived from the polyol (A) for obtaining the urethane prepolymer (F), the polyalkylene oxide (B) contained as needed, and the polyalkylene oxide (C) OH ) the amount of isocyanate groups derived from the isocyanate compound (D) relative to NCO ) ratio (M NCO / M OH) is less than 1.0. In particular, it is preferable that the ratio is 0.20 or more and 0.95 or less, and more preferably 0.20 or more and 0.70 or less, because it is easy to develop a viscosity suitable for coating and easy to develop a significantly high releasability due to high crosslinking. NCO / M OH ) represents the molar ratio. <Composition solution (H)> In order to facilitate handling of composition (G) or to obtain a desired viscosity or coatability, composition (G) can be mixed with an organic solvent to form a composition solution (H).

[0077] At this time, the composition solution (H) contains the composition (G) and an organic solvent.

[0078] The concentration of the composition (G) in the composition solution (H) is preferably 0.1% by mass or more and 90% by mass or less.

[0079] Examples of organic solvents include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide, N-methylpyrrolidone, and dimethylformamide. In terms of solubility and the boiling point of the organic solvent, ethyl acetate, toluene, methyl ethyl ketone, or a mixture thereof is particularly preferred. These solvents can be added at any stage, such as during the preparation of composition (G), dissolving or dispersing each raw material, or during synthesis.

[0080] The concentration of composition (G) in composition solution (H) is 0.1% by mass or more and 90% by mass or less, preferably 0.3% by mass or more and 50% by mass or less, and most preferably 0.5% by mass or more and 25% by mass or less. When the concentration is within this range, good coatability can be obtained even in a thin film when composition solution (H) is applied using a coater or the like, and the composition solution can be easily handled.

[0081] The viscosity of the composition solution (H) at 25°C is not particularly limited, but is 0.1 mPa·s or more and 100,000 mPa·s or less, preferably 1 mPa·s or more and 10,000 mPa·s or less, and more preferably 5 mPa·s or more and 1,000 mPa·s or less.

[0082] If the viscosity of the composition solution (H) at 25° C. is within this range, pinholes are less likely to occur when the composition solution is coated with a coater or the like and dried and cured, and smoothness is likely to be excellent, which is preferable. <Cured product (I)> The cured product (I) is the composition (G) or a reaction product of the composition (G) in the composition solution (H).

[0083] The cured product (I) can be obtained by reacting and curing (solidifying) the composition (G) or the composition solution (H) by various methods. The method for producing the cured product (I) is not particularly limited. For example, the cured product (I) can be produced by subjecting the composition (G) or the composition solution (H) to a self-condensation reaction or intermolecular reaction at room temperature or a high temperature of 170°C or less in the presence of, as needed, a catalyst, a solvent, an antioxidant, a light stabilizer, a leveling agent, a plasticizer, a release agent, a crosslinking agent, or other additives, followed by drying as needed. Among these, a reaction at a temperature of 130°C to 170°C for 1 to 30 minutes is preferred, as this increases the self-condensation property and tends to exhibit significantly higher release properties.

[0084] Here, the composition (G) or the composition solution (H) has remarkably excellent coatability when applied using a coater or the like, and therefore a coating film or sheet of the cured product (I) having a thin and uniform thickness can be obtained.

[0085] The thickness of the coating film of the cured product (I) is not particularly limited, but the thickness of the coating film is preferably from 0.001 μm to 100 μm, more preferably from 0.01 μm to 30 μm, in order to achieve a particularly good appearance of the coating film and to be less susceptible to brittle fracture and cure shrinkage.

[0086] The uses of the composition (G) and the cured product (I) obtained using the same are not particularly limited, and they can be used for any purpose, but they are preferably used in applications requiring easy peelability, releasability, curability, hardness, and strength, and specific examples include sealing materials for construction and civil engineering, adhesives such as elastic adhesives for construction, pressure-sensitive adhesives such as protective films, release agents, paints, elastomers, waterproof coatings, flooring materials, etc. In particular, the easy peelability and releasability of the resulting cured products are remarkably good, and therefore they can be preferably used in applications requiring easy peelability, such as compositions and coatings for release materials, compositions and adhesives for easy-release pressure-sensitive adhesives.

[0087] More preferably, because a thin film with smoothness with few pinholes and thickness unevenness is required, a release material composition for forming the release layer of a release sheet, a release material coating film obtained by curing the composition on a substrate, and a release sheet having a release layer made of the release material coating film on at least one side of the substrate are preferred. Among these, the production processes for semiconductor devices and ceramic green sheets require not only light releasability but also contamination resistance that does not contaminate the adherend, and smoothness with few pinholes and thickness unevenness, so the composition can be most suitably used as a release material composition, release material, and release sheet for use in the production processes for semiconductor devices and ceramic green sheets.

[0088] Such a release sheet is a sheet having a release layer made of the release material coating on at least one side of a substrate, and the method for producing it is not particularly limited, but it can be produced by coating composition (G) or composition solution (H) to a thickness of 0.01 μm or more and 50 μm or less on at least one side of a substrate such as a 15 to 200 μm PET film using a coater, and drying and curing for 3 to 60 minutes at a temperature in the range of 110°C to 180°C to form a release layer made of the release material coating on one side of the substrate, and aging as necessary. If the temperature exceeds 180°C and / or 60 minutes, the substrate will deteriorate, the formability of the release sheet will tend to deteriorate, and the release material layer may also deteriorate.

[0089] Among these, melamine crosslinking agents usually have six mononuclear functional groups, three of which are prone to react early, but the reaction rate of the remaining three functional groups is prone to change depending on the curing conditions. Therefore, it is preferable to apply the agent to a thickness of 0.01 μm to 20 μm and dry and cure it for 5 to 30 minutes at a temperature between 140°C and 170°C, as this allows the crosslinking to proceed and significantly improves the releasability. [Example]

[0090] The present invention will be explained in more detail below with reference to examples, but the present invention should not be construed as being limited to the following examples as long as the gist of the invention is not exceeded. The raw materials and evaluation methods used in the following examples and comparative examples are as follows. (Raw material 1) Polyol (Raw Material 1-1) Polyols (A1), (A2), and (A3) containing sugar residues with 6 or more carbon atoms per molecule, propylene oxide residues, and 4 or more hydroxyl groups. The polyol (A1) used was a commercially available sucrose-based polyol, O-855W, manufactured by Toho Chemical Industry Co., Ltd., with a nominal functionality of 8.0, a hydroxyl value of 377 mg KOH / g, a molecular weight of 1190, and a viscosity at 25°C of 15620 mPa·s.

[0091] The polyol (A2) used was Huntsman SG-522, a commercially available sucrose / glycerin polyol with a nominal functionality of 5.0, a hydroxyl value of 520 mg KOH / g, a molecular weight of 539, and a viscosity of 27,000 mPa·s at 25°C.

[0092] The polyol (A3) used was a commercially available sorbitol-based polyol, S-490 manufactured by Huntsman, with a nominal functionality of 4.7, a hydroxyl value of 490 mg KOH / g, a molecular weight of 538, and a viscosity of 9000 mPa·s at 25°C. (Raw Material 1-2) Polyol (AC) used in Comparative Example, which does not have a sugar residue having 6 or more carbon atoms The polyol (AC1) used was AR-2589, a commercially available tolylenediamine-based polyol manufactured by Toho Chemical Industry Co., Ltd., with a nominal functionality of 4.0, a hydroxyl value of 363 mg KOH / g, a molecular weight of 618, and a viscosity of 9350 mPa·s at 25°C.

[0093] The polyol (AC2) is a commercially available polycarbonate diol, and Nipporan 965 manufactured by Tosoh Corporation, having a nominal functionality of 2.0, a hydroxyl value of 113 mgKOH / g, and a molecular weight of 993, was used.

[0094] The polyol (AC3) used was a commercially available polytetramethylene glycol, PTG-1000SN manufactured by Hodogaya Chemical Co., Ltd., which has a nominal functionality of 2.0, a hydroxyl value of 112 mgKOH / g, and a molecular weight of 1002. (Raw Material 1-3) Polyalkylene oxide (B) having 2 to 3 hydroxyl groups per molecule and a number average molecular weight of 1500 or more The polyalkylene oxides (B1) and (B2) are polyoxypropylene glycol (diol) and polyoxypropylene glycol (triol), which have only propylene oxide groups as alkylene oxide groups and have two hydroxyl groups per molecule, respectively, synthesized by a conventional method using an imino group-containing phosphazenium salt (hereinafter referred to as IPZ catalyst) and triisopropoxyaluminum in combination. The polyalkylene oxide (B3) is a polyoxypropylene triol having three hydroxyl groups per molecule, obtained using a potassium hydroxide catalyst.

[0095] The polyalkylene oxide (B1) has a functionality of 2, a hydroxyl value of 20.8, a molecular weight of 5,400, and a degree of unsaturation of 0.0018 meq / g.

[0096] The polyalkylene oxide (B2) has a functionality of 3, a hydroxyl value of 24.0, a molecular weight of 7000, and a degree of unsaturation of 0.0028 meq / g.

[0097] The polyalkylene oxide (B3) has a functionality of 3, a hydroxyl value of 39.1, a molecular weight of 4,300, and a degree of unsaturation of 0.0553 meq / g. (Raw material 1-4) Polyalkylene oxide (C) containing one hydroxyl group and one ethylene oxide residue per molecule The polyalkylene oxide (C1) is a polyethylene glycol monomethyl ether having a functionality of 1, a hydroxyl value of 82.3, and a molecular weight of 682.

[0098] The polyalkylene oxide (C2) is a polyethylene glycol monomethyl ether having a functionality of 1, a hydroxyl value of 56.2, and a molecular weight of 1,002. (Raw material 2) Melamine crosslinker (F), other crosslinkers (FC) The melamine crosslinking agent (F1) is an imino group-containing alkylated melamine derivative obtained by alkylating the methylol group of commercially available imino group-containing methylol melamine. It has self-condensing properties, is alkylated only by methyl groups, has a nominal functionality of 6 in the mononuclear form, has a mononuclear ratio of 48% and is an isobutanol solution with a non-volatile content of 80%. Cymel 325N manufactured by Allnex Japan was used.

[0099] The melamine crosslinking agent (F2) is a commercially available imino group-containing methylol melamine derivative that is self-condensing, alkylated only by methyl groups, has a nominal functional group count of 6, a mononuclear ratio of 53%, and a non-volatile content of 82%. Cymel 701 manufactured by Allnex Japan was used as an isobutanol solution.

[0100] The melamine crosslinking agent (F3) used was Cymel 303LF manufactured by Allnex Japan, a commercially available fully alkylated melamine derivative in which the methylol groups have been completely alkylated. It has low self-condensation properties, alkylation is limited to methyl groups, the nominal number of functional groups in the mononuclear body is 6, the mononuclear body ratio is 60%, and the non-volatile content is 100%.

[0101] The crosslinking agent (FC1) used was Cymel 1123 manufactured by Allnex Japan, a commercially available benzoguanamine crosslinking agent that does not have a melamine structure but has a structure in which methylol groups are alkylated to amino groups, has a nominal functionality of 4, is alkylated with methyl and ethyl groups, and has a non-volatile content of 100%.

[0102] The crosslinking agent (FC2) used was C-HXR, a commercially available isocyanate crosslinking agent having an HDI isocyanurate structure, manufactured by Tosoh Corporation. (Raw Material 3) Isocyanate Compound (D) Used to Form Urethane Prepolymer The isocyanate compound (D1) is 1,6-hexamethylene diisocyanate (HDI). (Raw material 4) Additives In the examples and comparative examples, a melamine crosslinking acid catalyst and a urethanization catalyst were added as additives. The acid catalyst used was Cycat 602 manufactured by Allnex Japan, which has an aromatic sulfonic acid structure, and the urethanization catalyst used was dioctyltin dilaurate (abbreviation: DOTDL) manufactured by Wako Pure Chemical Industries, Ltd.

[0103] In the examples and comparative examples, X-22-170DX, a silicone-containing monool manufactured by Shin-Etsu Chemical Co., Ltd., was used. (Raw material 5) Solvent In the examples and comparative examples, when the composition solution (H) was used, methyl ethyl ketone manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used as the solvent. (Preparation of Compositions (G) and (GC)) In the examples and comparative examples, a predetermined amount of each raw material was placed in a 50 ml sample bottle, and the mixture was stirred and degassed at room temperature using a pencil mixer manufactured by AS ONE Corporation to obtain compositions (G) and (GC). (Preparation of composition solutions (H) and (HC)) In the examples and comparative examples, a predetermined amount of each raw material was placed in a 50 ml sample bottle, and the non-volatile content was adjusted to 20% using a solvent. The mixture was stirred and degassed at room temperature using a pencil mixer manufactured by AS ONE Corporation to obtain composition solutions (H) and (HC). (Preparation of Cured Product (I) and Sheet) The prepared compositions (G), (GC), and composition solutions (H), and (HC) were applied using a coater onto a 38 μm-thick, surface-untreated PET film (product name: Lumirror) manufactured by Toray Industries, Inc., so that the composition or composition solution would have a dry thickness of 10 μm or less. After coating, the film was left in an oven set to 145°C for 20 minutes to evaporate the solvent and cure, and then left to stand for one week in an environment of 23°C and 50% relative humidity to obtain a sheet in which a coating film of the cured product (I) was formed on the substrate. (Performance Evaluation of Compositions (G) and (GC), Composition Solutions (H) and (HC)) Cured products and sheets were prepared by the above-described methods using compositions (G) and (GC), or composition solutions (H) and (HC) when a solvent was used, and were evaluated for the following items. <Smoothness> ◎ (Passed smoothness): When visually observed, immediately after drying and curing, the entire coated surface is free of pinholes, the surface is smooth, and there is no thickness unevenness of 5% or more. ○ (Smoothness pass): When visually observed, there is thickness unevenness of 5% to 20% immediately after drying and curing, but the entire coated surface is smooth and free of pinholes. × (Failed smoothness): When visually inspected immediately after drying and curing, pinholes are found, thickness unevenness of the coating film exceeds 20%, or the surface of the coating film is rough. <Curability> ◎ (Passed curing): When there is absolutely no tackiness (stickiness) when touched with the fingers immediately after drying. ○ (Passed curing): If a slight tackiness (stickiness) is felt when touched with the fingers immediately after drying. △ (failed curing): There was a clear tackiness (stickiness) when touched with the fingers immediately after drying, which almost disappeared after leaving it for one week in an environment of 23°C and a relative humidity of 50%. × (failed curing): There is a clear tackiness (stickiness) when touched with the fingers immediately after drying, and the tackiness (stickiness) is still clear after leaving it for one week in an environment of 23°C and 50% relative humidity (poor curing). <Coatability> ◎ (Applicability passed): When visually observed, there is no repelling or liquid pooling, including at the edges, immediately after coating and immediately after drying and curing. ○ (Passed coatability): Visual observation shows that there are liquid pools or repelling at the edges immediately after coating and immediately after drying and curing, but no repelling inside the coated surface. × (Failed coatability): When visually observed, cissing is found inside the coated surface immediately after coating and immediately after drying and curing.

[0104] Those that passed the smoothness and curing tests were judged to be compositions that could be expected to be used in applications where releasability and easy peeling are required even in thin films.Furthermore, those that passed the coatability test were judged to have appropriate viscosity, good handleability, and excellent coating stability on an actual coating line. (Performance evaluation of cured products (I) and (IC)) The cured products and sheets obtained by the above-mentioned methods using compositions (G) and (GC), or composition solutions (H) and (HC) when a solvent was used, were evaluated according to the following criteria. <Mold releasability> A flat aluminum plate was attached to the substrate surface (not the cured coating surface) using double-sided tape. A 25 mm wide Nitto Denko 31B tape was attached to the cured coating surface on the substrate using a 5 kg roller and left to stand for 30 minutes at 23°C and 50% relative humidity. A tensile test was performed using an Orientec RTG-1210 tensile tester with a chuck distance of 13 cm and a pulling speed of 300 mm / min to measure the stress at peeling. Similarly, 31B tape was attached to the untreated surface of a PET substrate, and a peel test was performed. Evaluation was based on the following criteria. ◎ (Passed release): When the peel force is reduced to within the range of 0.1 to 50% compared to the stress when peeling 31B tape from the untreated surface of the PET substrate, and the difference between the maximum stress and minimum stress when peeling 31B tape from the cured coating surface is 15% or less. ○ (Passed releasability): When the peel force is reduced to between 50% and 80% of the stress when peeling 31B tape from the untreated surface of the PET substrate, and the difference between the maximum and minimum stress when peeling 31B tape from the cured coating surface is 15% or less. × (failed release): If the peel force was more than 80% of the stress when peeling 31B tape from the untreated surface of the PET substrate (insufficient release effect), or if the difference between the maximum stress and minimum stress when peeling 31B tape from the cured coating surface was more than 15% (difficult to impart stable release or easy release properties). <Wettability> The surface of a flat, alkali-free glass was wiped clean with acetone, and after drying, 0.5 cm of the edge of the cured coating film was attached to the glass. The hand was then released from a height of 1 cm and the area wetted under its own weight was evaluated according to the following criteria. ◎ (Passed wettability): In all three tests, 50% or more of the surface area was wetted by its own weight. ○ (Passed wettability): 1 to 2 times out of 3, 50% or more of the surface area gets wet under its own weight. × (failed wettability): 50% or more of the surface area did not get wet under its own weight in even one of the three tests.

[0105] Those that passed the release test were judged to be cured products that exhibit stable release and easy peelability, and release sheets using these were judged to be developable due to their excellent release properties.Furthermore, those that passed the wettability test were judged to be cured products with little misalignment or other molding defects, excellent molding stability, and flexible and resistant to breakage. <Examples and Comparative Examples> Example 1 is a composition solution (H1) prepared by adjusting the nonvolatile content of composition (G1) containing 80 parts by weight of polyol (A1), 20 parts by weight of melamine crosslinker (F1), and 1 part by weight of Cycat 302 as an acid catalyst to 20% using methyl ethyl ketone. Table 1 shows the results of Example 1. The curability and smoothness were good, and the release properties of the cured product (I) obtained from composition solution (H1) were remarkably good, suggesting that the composition solution (H1) can be used in applications requiring release properties and easy peelability.

[0106] In Examples 2 to 5, the types and composition ratios of the polyol (A) having a sugar residue with 6 or more carbon atoms and the melamine crosslinking agent (F) were changed, Example 2 did not contain an acid catalyst, and Examples 4 and 5 were composition (G) and composition solution (H) in which the non-volatile content was not adjusted by adding a solvent.

[0107] Table 1 shows the results of Examples 2 to 5. The curability and smoothness were good, and the releasability of the cured product (I) obtained from the composition (G) and the composition solution (H) was good.

[0108] Compared to Examples 4 and 5, which contained a melamine crosslinking agent (F3) with low self-condensation properties, Examples 1 to 3, which contained melamine crosslinking agents (F1) and (F2) containing self-condensing imino groups, had significantly better releasability.

[0109] Comparative Example 1 is a composition solution (HC1) containing a composition (GC1) containing a polyol (AC1) having a rigid aromatic amine residue instead of a polyol (A) having a sugar residue with 6 or more carbon atoms. The results of Comparative Example 1 are shown in Table 1. The composition solution was difficult to use due to poor curability and smoothness, and the cured product (IC1) obtained using it had insufficient releasability and could not be expected to be used in applications requiring easy releasability or releasability.

[0110] Comparative Example 2 is a composition (GC2) containing a polyol (AC2) having a polytetramethylene residue instead of polyol (A). The results are shown in Table 1. The composition solution had insufficient curability and was difficult to use, and the cured product (IC2) obtained using it had insufficient releasability and could not be expected to be used in applications requiring easy releasability or releasability.

[0111] Comparative Examples 3 and 4 are composition solutions (HC3, HC4) containing compositions (GC3, GC4) in which a guanamine crosslinker (FC1) and an isocyanate crosslinker (FC2), which have similar structures, were used instead of the melamine crosslinker (F). Table 1 shows the results of Comparative Examples 3 and 4. These composition solutions were difficult to use because they did not achieve both curability and smoothness. The cured products (IC3, IC4) obtained using these compositions both had insufficient releasability and were not suitable for use in applications requiring easy releasability or releasability.

[0112] Comparative Example 5 is a composition solution (HC5) that does not contain a polyol such as polyol (A) and contains a self-condensing melamine crosslinker (F1) and an acid catalyst composition (GC5). The results are shown in Table 1. Although the curability was good, the smoothness was poor and it was difficult to form a uniform coating film, making it difficult to use.

[0113] [Table 1]

[0114] Example 6 is a composition solution (H) containing a composition (G) to which polyalkylene oxide (B) was added in addition to the essential components polyol (A) and melamine crosslinker (F) in order to further improve wettability to the adherend. The results are shown in Table 2. While maintaining good curability and smoothness compared to Example 1, the cured product (I6) obtained from this composition solution (H6) had improved wettability to the adherend, was less susceptible to misalignment, and had good handleability, and is expected to be used in applications requiring releasability and easy peelability.

[0115] Furthermore, in Examples 7 to 9, polyalkylene oxide (C) was added to the compositions in order to further improve the smoothness during application and the releasability of the resulting cured product (I) compared to Example 6, and the smoothness during application and the releasability of the resulting cured product (I) were better.

[0116] In Example 10, there was a composition (G10) containing polyalkylene oxide (C) without adding polyalkylene oxide (B), and a solution of the composition (H10). The results are shown in Table 2. Compared to Example 1, the smoothness was improved, and the composition is expected to be applicable to applications requiring excellent productivity on an actual coating line, releasability, and easy peelability.

[0117] Comparative Example 6 is a composition solution (HC6) containing a composition (GC6) in which polyalkylene oxide (B) was added instead of polyol (A). The results are shown in Table 2. The composition solution had insufficient curability and was difficult to use, and the cured product (IC6) obtained using it had insufficient releasability and could not be expected to be used in applications requiring easy releasability or releasability.

[0118] Comparative Examples 7 and 8 are composition solutions (HC7, HC8) containing polyol (A), polyalkylene oxide (B), and polyalkylene oxide (C), and compositions (GC7, GC8) containing a guanamine crosslinking agent and an isocyanate crosslinking agent instead of the melamine crosslinking agent (F). The results are shown in Table 2. These composition solutions were difficult to use because they did not achieve both curability and smoothness, and the cured products (IC7, IC8) obtained using these compositions had insufficient releasability and were not suitable for use in applications requiring easy releasability or releasability.

[0119] [Table 2]

[0120] In Examples 11 to 14, in order to develop a suitable viscosity and further improve coatability, a urethane prepolymer (E) was formed in advance from a polyol (A) having a sugar residue of 6 or more carbon atoms and an isocyanate compound (D), and the composition contained at least the urethane prepolymer (E) and a melamine crosslinker (F). The results are shown in Table 3. As compared to Examples 6 to 10, the compositions had improved coatability, a suitable viscosity, good handling properties, excellent coating stability on an actual coating line, and productivity on an actual coating line. They are expected to be used in applications requiring good releasability and easy peelability.

[0121] Example 15 is a composition solution (H15) containing a composition (G15) to which a long-chain polyalkylene oxide (C) was added in addition to the urethane prepolymer (E) and melamine crosslinking agent (F) in order to improve the releasability compared to Example 14, but within a range that does not result in a decrease in handleability due to solidification. The results are shown in Table 3, and it was found that the releasability was improved compared to Example 14, and it is expected that this composition will be used in applications that require better releasability and easier peeling properties.

[0122] Example 16 is a composition solution (H16) containing a composition (G16) in which a very small amount of reactive silicone monool was added, while still achieving acceptable curability, smoothness, and coatability, in addition to the urethane prepolymer (E) and melamine crosslinker (F) in order to improve the release properties compared to Example 14. The results are shown in Table 3. Although a tendency toward a decrease in smoothness, coatability, and wettability was observed despite the addition of a very small amount, the release properties were still within a usable range, and the release properties were improved compared to Example 14, suggesting that the composition may be suitable for applications requiring release properties and easy peelability.

[0123] Comparative Example 9 is a composition solution (HC9) containing a composition (GC9) containing a urethane prepolymer (EC9) of a polyalkylene oxide (B1) containing no residue of polyol (A) and an isocyanate compound (D1) and a melamine crosslinker (F3), instead of the urethane prepolymer (E) of a polyol (A) having a sugar residue of 6 or more carbon atoms and an isocyanate compound (D). The results are shown in Table 3. The composition solution had insufficient curability and was difficult to use, and the cured product (IC9) obtained using it had insufficient releasability and was not expected to be used in applications requiring easy releasability or releasability.

[0124] Comparative Example 10 is a composition solution (HC10) containing a composition (GC10) that does not contain the urethane prepolymer (E) of polyol (A) and isocyanate compound (D) of Comparative Example 9, but contains a silicone compound to enhance releasability. The results are shown in Table 3. The composition solution was difficult to use because it had insufficient curability and significantly poor smoothness due to the inclusion of a silicone compound. The resulting cured product (IC10) also had high releasability, but significantly poorer wettability and poor molding stability.

[0125] Comparative Examples 11 and 12 are composition solutions (HC11, HC12) containing compositions (GC11, GC12) in which a guanamine crosslinking agent and an isocyanate crosslinking agent were added instead of the melamine crosslinking agent (F). The results are shown in Table 3. These composition solutions were difficult to use because they did not achieve both curability and smoothness, and the cured products (IC11, IC12) obtained using these compositions had insufficient releasability and were not suitable for use in applications requiring easy releasability or releasability.

[0126] Comparative Example 13 is a composition solution (HC13) containing a composition (GC13) containing a urethane prepolymer (EC13) of a polyol (AC1) having a rigid aromatic amine residue and an isocyanate compound (D1) and a melamine crosslinker (F1), instead of a urethane prepolymer (E) of a polyol (A) having a sugar residue with 6 or more carbon atoms and an isocyanate compound (D1). The results of Comparative Example 13 are shown in Table 3. The composition solution was difficult to use due to its poor curability and smoothness, and the cured product (IC13) obtained using it had insufficient release properties and was not suitable for use in applications requiring easy release or releasability.

[0127] [Table 3]

[0128] As shown above in the examples, the composition developed in this study has excellent curability and smoothness, and is capable of stably imparting releasability and easy release properties. It has been demonstrated that the composition can be suitably used in applications requiring easy release properties and easy release properties, such as release agent compositions and compositions for easy-release pressure sensitive adhesives.

[0129] In particular, since the composition can be used to form a thin coating film with high releasability on a substrate, the composition can be suitably used for release agent compositions and release materials used in the manufacturing processes of semiconductor devices and ceramic green sheets, as well as for release sheets having the release material layer on a substrate.

Claims

1. The composition comprises a polyol (A) containing a sugar residue having 6 or more carbon atoms in one molecule, an alkylene oxide residue, and 4 or more hydroxyl groups, and a melamine crosslinker (F), The composition (G) further comprises a polyalkylene oxide (B) having 2 to 3 hydroxyl groups per molecule, a number average molecular weight of 1500 or more, and a degree of unsaturation of 0.010 meq / g or less.

2. Composition (G) described in claim 1, wherein the mixing ratio of polyol (A) to polyalkylene oxide (B) is in the range of 10 / 90 to 70 / 30 by mass ratio.

3. The composition (G) according to claim 1 or claim 2, wherein the melamine crosslinking agent (F) comprises a methylolated melamine derivative or an alkylated melamine derivative thereof.

4. The composition (G) according to any one of claims 1 to 3, wherein the melamine crosslinking agent (F) has one or more imino groups and is self-condensing.

5. The composition (G) according to any one of claims 1 to 4, further comprising a polyalkylene oxide (C) having one hydroxyl group and an ethylene oxide residue per molecule and having a number average molecular weight in the range of 300 or more and less than 1,500.

6. The composition (G) according to any one of claims 1 to 5, further comprising a urethane prepolymer (E) which is a reaction product of the polyol (A) and an isocyanate compound (D).

7. The urethane prepolymer (E) has a weight average molecular weight of 1,000 or more and at least one hydroxyl group in each molecule, The composition (G) according to claim 6, characterized in that the weight ratio of the urethane prepolymer (E) to the melamine crosslinking agent (F) is in the range of 30 / 70 to 95 / 5.

8. A composition solution (H) comprising the composition (G) according to any one of claims 1 to 7 and an organic solvent.

9. A cured product (I) comprising a reaction product of the composition (G) according to any one of claims 1 to 7.

10. A release coating film comprising the cured product (I) according to claim 9.

11. A release sheet having a release material layer comprising the release material coating film according to claim 10 on at least one surface of a substrate.

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