Polyalkylene glycol mono (METH) acrylate and polymer thereof, and film composition

Abstract

The present invention provides a polyalkylene glycol mono(meth)acrylate and its polymer, as well as a film composition containing the aforementioned polyalkylene glycol mono(meth)acrylate. The polyalkylene glycol mono(meth)acrylate is represented by the following formula (1), and the ratio wb / wf, which can be calculated from the chromatogram obtained by gel permeation chromatography, satisfies the relationship of the following formula (2). CH2=CR-COO-(AO)nH 0.25 ≤ wb / wf ≤ 0.90 The notations in equations (1) and (2) are defined as described in the specification. The present invention provides a polyalkylene glycol mono (meth) acrylate which is represented by the formula (1): CH2 = CR-COO-(AO)nH, and has a ratio wb / wf of wb and wf calculated from the chromatogram obtained by gel permeation chromatography measurement satisfing the relationship of the formula (2): 0.25 ≤ wb / wf ≤ 0.90 (the definitions of the symbols in the formulas (1) and (2) are as described in the specification); a polymer thereof, and a film composition.

Description

[Technical Field]

[0001] This invention relates to polyalkylene glycol mono(meth)acrylate and its polymers, as well as compositions for use in films. Here, "compositions for use in films" refers to compositions that can be used to form films. [Previous Technology]

[0002] Polyalkyldiol mono(meth)acrylate (hereinafter also referred to as "PAG mono(meth)acrylate") has polymerizable functional groups, so it can be used as a raw material for acrylic resins or photocurable resins. In addition, PAG mono(meth)acrylate can be used in various applications such as photosensitive resins, coatings, adhesives, binders, paints, inks, rubber or thermoplastic elastomers.

[0003] By controlling the average additional mole number or additional form per mole equivalent of ethylene oxide (EO) or propylene oxide (PO), the hydrophilicity or hydrophobicity of PAG mono(meth)acrylate can be modified. Furthermore, by using PAG mono(meth)acrylate as a raw material for various materials, various materials can be endowed with softness, flexibility, elasticity, strain resistance, and adhesion.

[0004] For example, conventional acrylic resins that can be used on films have the disadvantage of low flexibility. However, flexible films can be formed from compositions containing PAG mono(meth)acrylate.

[0005] Various technologies have been developed for PAG mono(meth)acrylate. For example, the method for manufacturing polyalkylene glycol mono(meth)acrylate described in Patent Document 1 involves using a boron trifluoride compound as a catalyst to perform ring-opening polymerization of ethylene oxide in 2-hydroxyethyl acrylate, then adding an adsorbent to remove the boron trifluoride compound, and treating the mixture at 0 to 50°C.

[0006] Furthermore, the method for manufacturing the polymer described in Patent Document 2 involves reacting (meth)acrylic acid with an epoxide in the presence of a catalyst to synthesize (meth)propionate ester represented by the following formula (I).

[0006] CH2=C(R1)-COO-(R2O)nH (I)

[0006] (The symbols in formula (I) are as described in Patent Document 2)

[0006] A method for manufacturing a polymer by polymerizing the obtained (methyl)propionate. Also, the above formula (I) is described as "Formula (1)" in Patent Document 2.

[0006] [Previous Technical Documents]

[0006] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2005-281274

[0007] [Patent Document 2] Japanese Patent Application Publication No. 2006-070147

[0008] Polymers obtained by polymerizing conventional PAG mono(meth)acrylates do not have sufficient properties (e.g., strain resistance). Furthermore, in the production of polymers by polymerizing conventional PAG mono(meth)acrylates, gelation of the product occurs, resulting in a decrease in the quality and function of the product, as well as a decrease in yield.

[0009] Furthermore, to increase the hardness of the obtained film, a large amount of multifunctional monomers can be incorporated into the film composition. In the manufacture of a film using a film composition containing multifunctional monomers, the film is hardened after it has been formed from the aforementioned film composition. If the aforementioned film composition becomes viscous during storage, the conditions during film manufacturing (especially during film formation) must be changed. Therefore, there is a need for film compositions that are difficult to become viscous during storage.

[0010] The object of the present invention is to provide a polyalkylene glycol mono(meth)acrylate that can suppress gelation during polymer manufacturing. Furthermore, the object of the present invention is to provide a polyalkylene glycol mono(meth)acrylate that yields a polymer with excellent strain resistance. Additionally, another object of the present invention is to provide a composition for films that are difficult to tackify during storage.

[0011] Based on in-depth research in view of the above-mentioned matters, the inventors have discovered a polyalkylene glycol mono(meth)acrylate and its polymer, as well as a film composition containing the aforementioned polyalkylene glycol mono(meth)acrylate, thereby solving the above-mentioned problems. The polyalkylene glycol mono(meth)acrylate exhibits asymmetrical dissolution peaks in the chromatogram obtained by gel permeation chromatography, with the molecular weight distribution biased towards the high molecular weight side.

[0012] That is, the present invention is as follows.

[0012] [1] A polyalkylene glycol mono(meth)acrylate is represented by the following formula (1), and the ratio wb / wf, which can be calculated from the chromatogram obtained by gel permeation chromatography, satisfies the following relationship (1).

[0012] CH2=CR-COO-(AO)n-H

[0012] (In formula (1), R represents a hydrogen atom or a methyl group, AO represents at least one oxyalkylene group having 2 to 4 carbon atoms. When there are two or more AOs, the addition pattern of (AO)n can be either block or random, and n represents the average number of moles of oxyalkylene groups added, which is 5 to 100.)

[0012] 0.25≦wb / wf≦0.90 (2)

[0012] (In formula (2), among the peaks in the chromatogram, when the retention time at the maximum peak height (h) is set as th, and the two retention times at 1 / 10 of the maximum peak height (h1 / 10) are set as tf and tb (where tf < tb), wf represents the difference between th and tf (th - tf), and wb represents the difference between tb and th (tb - th).)

[0012] [2] The polyalkylene glycol mono(meth)acrylate as described in [1] above, wherein AO in formula (1) is one or two oxyalkylene groups having 2 or 3 carbon atoms.

[0012] [3] A polymer obtained by polymerizing the polyalkylene glycol mono(meth)acrylate as described in [1] or [2] above.

[0012] [4] A composition for a film, which is a composition for a film containing the following components (A) and (B), wherein

[0012] Based on the total of components (A) and (B), the content of component (A) is 20 to 50% by weight,

[0012] Based on the total of components (A) and (B), the content of component (B) is 50 to 80% by weight,

[0012] Component (A): The polyalkylene glycol mono(meth)acrylate as described in [1] or [2] above, and

[0012] Component (B): A polyfunctional (meth)acrylate monomer.

[0013] The polyalkylene glycol mono(meth)acrylate of the present invention has an excellent effect of suppressing gelation in the production of polymers. In addition, the polymer obtained from the polyalkylene glycol mono(meth)acrylate of the present invention has good strain resistance and is suitable as a raw material for coating films and the like. In addition, the film composition containing the polyalkylene glycol mono(meth)acrylate and polyfunctional (meth)acrylate monomer of the present invention is not likely to increase in viscosity during storage.

Brief Description of Drawings

[0015] FIG. 1 is a chromatogram pattern for explaining that wf and wb can be obtained by gel permeation chromatography measurement of polyalkylene glycol mono(meth)acrylate.

Embodiments

[0016] In this specification, the numerical range defined using "to" includes the numerical values at both ends (upper limit and lower limit) of "to". For example, "2 to 4" means 2 or more and 4 or less.

[0016] In this specification, "(meth)acrylate" means acrylate or methacrylate. Here, one kind of (meth)acrylate may be used alone, or two or more kinds may be used simultaneously. Terms such as "(meth)acryloyl" have the same meaning as "(meth)acrylate".

[0017] <PAG mono(meth)acrylate>

[0017] The PAG mono(meth)acrylate of the present invention is a compound represented by formula (1):

[0017] CH2=CR-COO-(AO)n-H (1)

[0017] (In formula (1), R represents a hydrogen atom or a methyl group, AO represents at least one oxyalkylene group having 2 to 4 carbon atoms. When there are two or more kinds of AO, the additional form of (AO)n can be either block or random, and n represents the average additional molar number of oxyalkylene groups, which is 5 to 100).

[0018] AO is at least one oxyalkylene group having 2 to 4 carbon atoms. That is, AO is at least one selected from the group consisting of oxyethylene group, oxypropylene group, and oxybutylene group. AO is preferably one or two kinds of oxyalkylene groups having 2 or 3 carbon atoms, more preferably oxypropylene group. n is the average additional molar number of oxyalkylene groups. Therefore, n can have a decimal. n is preferably 5 to 60, more preferably 5 to 50, still more preferably 5 to 40, and particularly preferably 15 to 40. 2] 3]

[0019] <Characteristics in Gel Permeation Chromatography Analysis of PAG Mono(meth)acrylate>

[0019] The PAG mono(meth)acrylate of the present invention is characterized in that the ratio wb / wf of wb to wf calculated from the chromatogram (vertical axis: refractive index intensity, horizontal axis: retention time) obtained by gel permeation chromatography (GPC) using a differential refractometer satisfies the following relationship of formula (2):

[0019] 0.25 ≦ wb / wf ≦ 0.90 (2)

[0019] (In formula (2), in the peaks of the chromatogram, when the retention time at the maximum peak height (h) is set as th, and the two retention times at 1 / 10 of the maximum peak height (h1 / 10) are set as tf and tb (where tf < tb), wf represents the difference between th and tf (th - tf), and wb represents the difference between tb and th (tb - th).)

[0020] When wb / wf is less than 0.25, it is possible that the molecular weight distribution of the PAG mono(meth)acrylate is greatly biased towards the high molecular weight side, the concentration of the polymerizable functional group becomes low, and the polymerization property of the PAG mono(meth)acrylate decreases. From the viewpoint of polymerization property, wb / wf is preferably 0.30 or more, more preferably 0.35 or more.

[0021] On the other hand, when wb / wf is greater than 0.90, it is easy to gel the PAG mono(meth)acrylate itself of the present invention and the reaction solution containing the PAG mono(meth)acrylate of the present invention. In addition, when wb / wf is greater than 0.90, the strain resistance of the polymer obtained by polymerizing the PAG mono(meth)acrylate of the present invention is insufficient. Here, "strain resistance" refers to the property that the shape or volume changed by applying an external force to an object returns to the original state after removing the external force. From the viewpoints of suppressing gelation and strain resistance, wb / wf is preferably 0.80 or less, more preferably 0.60 or less.

[0022] In the present invention, the chromatogram (vertical axis: refractive index intensity, horizontal axis: retention time) for calculating wb / wf is obtained by continuously installing three columns with HLC - 8320GPC (registered trademark) as the gel permeation chromatography (GPC) system, SHODEX KF - G as the guard column, and SHODEX KF804L as the separation column, with the separation column temperature at 40°C, using tetrahydrofuran as the developing solvent, flowing at a flow rate of 1 mL per minute, injecting 0.1 mL of a 0.1 wt% tetrahydrofuran solution of PAG mono(meth)acrylate, and using the EcoSEC GPC calculation program.

[0023] <Manufacture of PAG mono(meth)acrylate>

[0023] The PAG mono(meth)acrylate of the present invention can be manufactured by adding ethylene oxide, propylene oxide, and butane oxide (preferably propylene oxide) to a starting material (e.g., 2-hydroxypropyl methacrylate) in the presence of a complex metal cyanide catalyst (hereinafter also referred to as "DMC catalyst"). Specifically, the starting material and DMC catalyst are added to a reaction vessel, and ethylene oxide, propylene oxide, and butane oxide (hereinafter collectively referred to as "2- to 4-carbon alkyl oxides") are continuously or intermittently added under stirring in an inert gas environment for addition polymerization. The 2- to 4-carbon alkyl oxides can be added under pressure or at atmospheric pressure.

[0024] There is no limitation on the average supply rate of the 2- to 4-carbon epoxides, but it is desirable to vary it according to the amount of 2- to 4-carbon epoxides fed in. Specifically, when the supply rate (supply per unit time) for the total supply of 2- to 4-carbon epoxides is set to V1 for a period of 5% to 20% by weight, the supply rate for the total supply of 2- to 4-carbon epoxides is set to V2 for a period of 20% to 50% by weight, and the supply rate for the total supply of 2- to 4-carbon epoxides is set to V3 for a period of 50% to 100% by weight, in the manufacture of a sample of PAG mono(meth)acrylate of the present invention, it is preferable to control the average supply rate of the 2- to 4-carbon epoxides to such that V1 / V2 = 1.1 to 2.0 and V2 / V3 = 1.1 to 1.5. Furthermore, in another embodiment of the PAG mono(meth)acrylate of the present invention, it is preferable to control the average supply rate of the 2- to 4-carbon alkyl oxide to such that V1 / V2 = 0.4 to 0.9 and V2 / V3 = 0.5 to 0.95.

[0025] Furthermore, the reaction temperature for attaching 2- to 4-carbon alkyl oxides to the starting materials is preferably 50 to 120°C, and more preferably 70 to 90°C. If the reaction temperature is below 50°C, the reaction rate will become very slow, and if it is above 120°C, problems such as polymerization of polymerizable groups in the starting materials or coloring will occur.

[0026] Although there are no particular restrictions on the trace amount of water contained in the starting materials and the epoxides with 2 to 4 carbon atoms, it is desirable that the water content in the starting materials is 0.5% by weight or less, and the water content in the epoxides with 2 to 4 carbon atoms is 0.01% by weight or less.

[0027] While there is no particular limitation on the amount of DMC catalyst used, it is preferable to use 0.000 to 0.1 parts by weight, and more preferably 0.001 to 0.05 parts by weight, relative to 100 parts by weight of the generated epoxide derivative. The DMC catalyst can be added to the reaction system all at once at the beginning, or it can be added sequentially in stages. After the polymerization reaction is completed, the DMC catalyst is removed. Catalyst removal can be carried out by conventional methods such as filtration separation, centrifugation, or treatment with synthetic adsorbents.

[0028] In the manufacture of PAG mono(meth)acrylate, conventional DMC catalysts may be used. DMC catalysts may be, for example, those shown in formula (3) below:

[0028] Ma[M'x(CN)y]b(H2O)c‧(L)d (3)

[0028] (In formula (3), M and M' represent metal atoms, L represents organic ligands, and a, b, c, d, x and y represent positive integers.)

[0029] Examples of metal atoms (metal cations) M include: Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV), W(VI), etc. Among these, Zn(II) is preferred.

[0030] Examples of metal atoms (metal cations) M' include: Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ni(II), V(IV), V(V), etc. Among these, Fe(II), Fe(III), Co(II), and Co(III) are preferred.

[0031] Organic ligand L can be, for example, alcohols, ethers, ketones, esters, etc., with alcohols being preferred. Preferred organic ligands are water-soluble, and specific examples include butanol, n-butanol, isobutanol, N,N-dimethylacetamide, ethylene glycol dimethyl ether (glycol dimethyl ether), diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), etc. Particularly preferred DMC catalyst system is Zn(II)3[Co(III)(CN)6]2(H2O)4(terbutanol)2, which is coordinated with butanol.

[0032] In the reaction of the 2- to 4-carbon alkyl oxides with addition of the starting material, other additives may be used without prejudice to the characteristics of the present invention. For example, as polymerization inhibitors, hydroquinone (HQ), hydroquinone monomethyl ether (MQ), 2,6-di-tert-butylhydroxytoluene (BHT), di-tert-butylanisole (BHA), α-tocopherol, β-tocopherol, γ-tocopherol, etc., may be added to the reaction system. MQ and / or BHT are preferred polymerization inhibitors, with BHT being more preferred. The amount of polymerization inhibitor added is preferably 0.001 to 0.3 parts by weight relative to 100 parts by weight of the total amount of the starting material (e.g., 2-hydroxypropyl methacrylate) and the 2- to 4-carbon alkyl oxides. When the amount added is less than 0.001 parts by weight, the function of the polymerization inhibitor will be insufficient, and gelation may occur during the addition of the 2- to 4-carbon alkyl oxides. On the other hand, adding more than 0.3 parts by weight may reduce the purity of the obtained PAG mono(meth)acrylate.

[0033] <Polymer>

[0033] This invention provides a polymer obtained by polymerizing the above-mentioned PAG mono(meth)acrylate. The polymer may be obtained by polymerizing only PAG mono(meth)acrylate, or by copolymerizing PAG mono(meth)acrylate with other polymerizable compounds. Examples of other polymerizable compounds include: methyl acrylate, methyl methacrylate, and other (meth)acrylates without PAG chains, acrylonitrile, methacrylonitrile, styrene, butadiene, etc. While the amount of PAG mono(meth)acrylate used during polymerization may vary depending on the application, it is preferably 10% by weight or more, more preferably 20% by weight or more, more preferably 30% by weight or more, and particularly preferably 50% by weight or more and 100% by weight or less, relative to the total amount of PAG mono(meth)acrylate and other polymerizable compounds.

[0034] To obtain the polymer of the present invention, solution polymerization, emulsion polymerization, bulk polymerization, etc., may be appropriately selected. Polymerization can be carried out using conventional methods (e.g., thermal polymerization, photopolymerization, electron beam polymerization). When obtaining the polymer of the present invention, it is preferable to use a polymerization initiator (thermal polymerization initiator or photopolymerization initiator). Only one polymerization initiator may be used, or two or more may be used in combination.

[0035] Examples of thermal polymerization initiators include: tributyl peroxytrimethylacetate, trihexyl peroxytrimethylacetate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-bis(tert-butylperoxy)octane, n-butyl-4,4-bis(tert-butylperoxy)valerate, tert-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-disperoxide, di-tert-butyl peroxide, tert-butyl isopropylbenzene peroxide, diisopropylbenzene peroxide, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, benzoyl peroxide, etc. Oxides, organic peroxides such as tert-butylperoxyisopropyl carbonate, or 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylpentanitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(aminomethoxyazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylpentanitrile, 2,2'-azobis(2-methyl-N-phenylpropanediamine) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropanediamine] dihydrochloride, 2,2'-azobis[N-hydroxyphenyl]-2-methyl [2,2'-Azobis[2-methyl-N-(phenylmethyl)propamidine] dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propamidine] dihydrochloride, 2,2'-Azobis(2-methylpropamidine) dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)-2-methylpropamidine] dihydrochloride, 2,2'-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepine-2-yl)propane] dihydrochloride, 2,2'- 2,2'-Azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl]propane, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propane}, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propane}, 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propane], 2,Azo compounds include 2'-azobis(2-methylpropionic acid) dihydrate, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanopentanoic acid), and 2,2'-azobis[2-(hydroxymethyl)propionitrile].

[0036] Thermal polymerization using a thermal polymerization initiator can be carried out within the normally operating temperature range and polymerization time. The amount of thermal polymerization initiator used is usually 0.0001 mol to 0.1 mol relative to 1 mol of the polymerizable functional group ((meth)acrylyl). It is more preferably 0.001 mol to 0.1 mol, and even more preferably 0.005 mol to 0.1 mol.

[0037] Examples of photopolymerization initiators include: 1-hydroxycyclohexane-1-ylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-1-N-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino- Alkyl phenyl ketones such as 1-(4-morpholinylphenyl)butanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxides, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxides and other alkylphosphine oxides, 1,3-bis(tert-butyldioxycarbonyl)benzene, 3,3',4,4'-tetra(tert-butyldioxycarbonyl)diphenyl ketone and other aromatic peroxide esters.

[0038] Photopolymerization can be carried out within the wavelength range and irradiation time of commonly used light. The amount of photopolymerization initiator used is typically 0.0001 mol to 0.1 mol relative to 1 mol of the polymerizable functional group (methyl(acrylic) group), preferably 0.001 mol to 0.1 mol, and even more preferably 0.005 mol to 0.1 mol. Sensitization of pigments can be performed during photopolymerization.

[0039] From the viewpoint of improving strain resistance, the weight-average molecular weight of the polymer of the present invention is preferably 3,000 to 5,000,000, more preferably 4,000 to 4,000,000, and even more preferably 5,000 to 3,000,000. The aforementioned weight-average molecular weight is a value measured by a gel permeation chromatography apparatus under the above conditions.

[0040] <Compositions for Thin Films>

[0040] This invention provides a composition for thin films, which is a composition for thin films containing the following components (A) and (B), wherein,

[0040] The content of component (A) is 20 to 50% by weight relative to the total of components (A) and (B), and

[0040] The content of component (B) is 50 to 80% by weight relative to the total of components (A) and (B):

[0040] (Component (A)) The PAG mono(meth)acrylate of the present invention that satisfies the above requirements, and

[0040] (Component (B)) Polyfunctional (meth)acrylate monomer.

[0041] <Component (A)>

[0041] Component (A) of the film composition of the present invention is the PAG mono(meth)acrylate of the present invention. The description of the PAG mono(meth)acrylate of the present invention is as described above. The PAG mono(meth)acrylate of the present invention may use only one type, or two or more types may be used in combination.

[0042] From the viewpoint of suppressing thickening, the content of component (A) is preferably 20 to 50% by weight, and more preferably 25 to 50% by weight, and more preferably 30 to 50% by weight, relative to the total of components (A) and (B). Furthermore, from the viewpoint of suppressing thickening, the content of component (A) is preferably 10 to 50% by weight, and more preferably 20 to 50% by weight, relative to the composition as a whole.

[0043] <Ingredient (B)>

[0043] Component (B) of the film composition of the present invention is a polyfunctional (meth)acrylate monomer, which is a component that improves the curability of the film composition. Here, "polyfunctional (meth)acrylate" refers to a (meth)acrylate having two or more (meth)acrylic groups in one molecule. Furthermore, "difunctional (meth)acrylate" as described later refers to a (meth)acrylate having two (meth)acrylic groups in one molecule. "Trifunctional (meth)acrylate" and the like have the same meaning as "difunctional (meth)acrylate".

[0044] Component (B) may be used in combination with only one type or in combination with two or more types. Examples of component (B) include: ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, and other alkyl diol dimethacrylates; polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, and other polyalkylene glycol dimethacrylates; neopentyl glycol dimethacrylate, tricyclodecanediethanol dimethacrylate, polycarbonate glycol dimethacrylate, polyester glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, etc. The following are difunctional (meth)acrylates other than propoxylated bisphenol A dimethacrylate, polyurethane dimethacrylate, and other alkyl diol dimethacrylates and polyalkyl diol dimethacrylates; trifunctional (meth)acrylates such as trimethylolpropane trimethacrylate, ethoxylated isocyanurate trimethacrylate, and ε-caprolactone-modified tri((meth)acryloxyethyl)isocyanurate; quadrfunctional (meth)acrylates such as di-trimethylolpropane tetramethacrylate; pentafunctional (meth)acrylates such as dinepentylenetetrol pentamethacrylate; and hexafunctional (meth)acrylates such as dinepentylenetetrol hexamethacrylate. Among these, alkyl diol dimethacrylates are preferred, and butanediol dimethacrylates are even more preferred.

[0045] From the viewpoint of hardening, the content of component (B) is 50 to 80% by weight, preferably 50 to 75% by weight, and even more preferably 50 to 70% by weight, relative to the total of component (A) and component (B).

[0046] <Polymerization Initiator>

[0046] The thin film composition of the present invention preferably contains a polymerization initiator. Only one polymerization initiator may be used, or two or more may be used in combination. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator. Only one thermal polymerization initiator and one photopolymerization initiator may be used, or two or more may be used in combination. Examples of thermal polymerization initiators and photopolymerization initiators include those described above.

[0047] The content of the polymerization initiator is preferably 0.0001 mol or more and 0.1 mol or less, more preferably 0.001 mol or more and 0.1 mol or less, and even more preferably 0.005 mol or more and 0.1 mol or less, relative to 1 mol of the polymerizable functional group ((meth)acrylyl) in the film composition of the present invention.

[0048] <Monofunctional (meth)acrylate monomer>

[0048] From the viewpoint of suppressing thickening, the film composition system of the present invention is preferably composed of monofunctional (meth)acrylate monomers other than polyalkylene glycol mono(meth)acrylate.

[0049] A single monofunctional (meth)acrylate monomer may be used, or two or more may be used in combination. Examples of monofunctional (meth)acrylate monomers include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, stearyl methacrylate, phenyl methacrylate, methyl methacrylate, isoborneol methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, tributylcyclohexyl methacrylate, and 1-adamantane methacrylate. Among these, methyl methacrylate is preferred.

[0050] When using monofunctional (meth)acrylate monomers, the content of the monomer relative to 100 parts by weight of component (B) is preferably 10 to 40 parts by weight, more preferably 15 to 40 parts by weight, and even more preferably 20 to 40 parts by weight.

[0051] <Other Ingredients>

[0051] The film composition of the present invention may contain other components different from components (A), (B), polymerization initiators, and monofunctional (meth)acrylates, without impairing the effects of the present invention. Examples of other components include: carboxyl-containing resins, (meth)acrylate resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, phenolic resins, cresol resins, antistatic agents, antioxidants, rubber, silicon dioxide particles, zirconium oxide, plasticizers, ultraviolet absorbers, defoamers, thixotropic agents, release agents, fillers, phosphors, pigments, etc. Only one of these other components may be used, or two or more may be used in combination.

[0052] The content of other components relative to the overall composition is preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less. Here, "the content of other components is 20% by weight or less relative to the overall composition" means that the film composition of the present invention does not contain other components, or contains other components at 20% by weight or less relative to the overall composition. Other similar expressions have the same meaning.

[0053] <Applications of Thin Films>

[0053] Examples of applications of the thin films obtained from the thin film composition of the present invention include: light-emitting diode modules, mobile phones, smartphones, tablet computers, personal computers, cameras, organic electroluminescent (organic EL) elements, flat panel displays, touch panels, electronic paper, photodiodes, photoelectric crystals, solar cells, dry film resists, projectors, home appliances, automobiles, motorcycles, heavy machinery, railway vehicles, ships, building materials, smoke-proof wall panels, smoke-proof curtains, decorative panels, and other components.

[0053] [Example]

[0054] Hereinafter, examples and the like will be listed to describe the present invention in detail.

[0055] Synthesis Example 1: Synthesis of a complex metal cyanide complex (DMC) catalyst

[0055] A 15 mL aqueous solution containing 0.84 g of potassium hexacyanocobalaminate (K3Co(CN)6) was stirred at 40°C and then added dropwise over 15 minutes to a 2.0 mL aqueous solution containing 2.1 g of zinc chloride. After the addition was complete, 16 mL of water and 16 g of tributanol were added, the temperature was raised to 70°C, and the mixture was stirred for 1 hour. After cooling to room temperature, the mixture was filtered (first time) to obtain a solid. 14 mL of water and 8.0 g of tributanol were added to this solid, and the mixture was stirred for 30 minutes. The mixture was then filtered (second time) to obtain another solid.

[0056] Add 18.6g of tributanol and 1.2g of methanol to the obtained solid, stir for 30 minutes, and then perform filtration (3rd time). Dry the obtained solid at 40°C and under reduced pressure for 3 hours to obtain 0.7g of DMC catalyst (Zn(II)3[Co(III)(CN)6]2(H2O)4(tributanol)2).

[0057] Example 1: Synthesis of Compound 1

[0057] In a 5-liter (4,890 mL) stainless steel pressure-resistant reaction vessel equipped with a thermometer, pressure gauge, safety valve, nitrogen purge pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket, 500 g of 2-hydroxypropyl methacrylate (0.02 wt% water), 0.3 g of DMC catalyst obtained in the same manner as in Synthesis Example 1, and 0.6 g of 2,6-di-tert-butylhydroxytoluene (BHT) were fed in. After replacing the nitrogen gas, the temperature was raised to 70°C, and while stirring at a pressure below 0.3 MPa, 403 g of propylene oxide (methyl ethylene oxide, 0.005 wt% water) was dripped in through the nitrogen purge pipe. After observing the pressure and temperature changes in the reaction vessel over time, the pressure in the reaction vessel was rapidly reduced 5 hours after the dripping of 403 g of propylene oxide. Then, while maintaining the reaction vessel at 70°C, 1,132 g of propylene oxide was slowly dripped in through a nitrogen purge tube under conditions below 0.5 MPa. The average feed rates were V1 = 260 g / h, V2 = 203 g / h, and V3 = 152 g / h (V1 / V2 = 1.28, V2 / V3 = 1.34). After the dripping was complete, the mixture was allowed to react at 70°C for 0.5 hours. The reaction mixture was then removed from the reaction chamber and filtered to remove solids, yielding a liquid compound 1. Compound 1 was analyzed using a gel permeation chromatography apparatus (HLC-8320GPC, registered trademark) as described above.

[0058] Examples 2 to 4: Synthesis of compounds 2 to 4

[0058] Except for the additional mole number of propylene oxide, or the additional mole number of propylene oxide and the starting materials, compounds 2 to 4 were synthesized by the same method as that used for the synthesis of compound 1. The resulting compounds 2 to 4 were then subjected to gel permeation chromatography analysis in the same manner as described above.

[0059] Examples 5 to 8: Synthesis of compounds 5 to 7

[0059] Compounds 5 to 7 were synthesized using the same method as that used in the synthesis of compound 1, except that ethylene oxide and propylene oxide, or 1,2-epoxybutane were used instead of propylene oxide as the epoxide, the additional mole number of the epoxide was changed, and the starting materials described in Table 1 below were used. Compounds 5 to 7 were then subjected to gel permeation chromatography analysis in the same manner as described above. Furthermore, in Example 5, propylene oxide was first added to the starting material, and then a mixture of ethylene oxide and propylene oxide was added to synthesize compound 5, which was in an atactic form of (AO)n. In addition, in Example 6, compound 6, which was in a block form of (AO)n, was synthesized by first adding propylene oxide to the starting material, and then adding ethylene oxide.

[0060] Comparative Example 1: Synthesis of Compound 8

[0060] In a 5-liter (4,890 mL) stainless steel pressure-resistant reaction apparatus equipped with a thermometer, pressure gauge, safety valve, nitrogen purge pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket, 500 g of 2-hydroxypropyl methacrylate, 17.6 g of boron trifluoride diethyl ether complex, and 0.6 g of hydroquinone monomethyl ether (MQ) were fed in. After replacing the nitrogen gas, the mixture was heated to 60°C and stirred at a pressure below 0.3 MPa. Meanwhile, 1,578 g of propylene oxide (methyl ethylene oxide) was added dropwise through the nitrogen purge pipe. After the addition was complete, the mixture was allowed to react at 60°C for 0.5 hours. Water and hexane were added, followed by neutralization with an aqueous sodium hydroxide solution. After removing the aqueous layer, the hexane and water were distilled off under reduced pressure. The concentrate was filtered to remove the solid, yielding a liquid compound 8. The same procedure as described above was performed, and the resulting compound 8 was analyzed using a gel permeation chromatography apparatus.

[0061] Comparative Examples 2 and 3: Synthesis of Compounds 9 and 10

[0061] Except for the additional mole number of propylene oxide, or the additional mole number of propylene oxide and the starting materials, compounds 9 and 10 were synthesized by the same method as that used for the synthesis of compound 8. The same operations as described above were performed, and the resulting compounds 9 and 10 were measured by gel permeation chromatography.

[0062] The starting materials used in the synthesis of compounds 1 to 10, the wb / wf obtained from the chromatograms of compounds 1 to 10, and the characteristics of compounds 1 to 10 are presented in Table 1. However, the molecular weights were calculated by measuring the hydroxyl valence according to JIS K-1557-1j.

[0063] [Table 1]

[0064] (Assessment of inhibition of gelation 1)

[0064] The gelation inhibition of compound 1 obtained in Example 1 and compound 8 obtained in Comparative Example 1 was evaluated. Specifically, 15g of the aforementioned compound was weighed into a spiral tube, and the spiral tube containing the aforementioned compound was placed into a constant temperature bath at 150°C under a nitrogen atmosphere. The time from the time the spiral tube was placed into the constant temperature bath until the aforementioned compound gelled (gelation time) was measured. After the spiral tube was placed into the constant temperature bath, the state of the compound in the spiral tube was checked every 10 minutes (maximum: 180 minutes). When the spiral tube was horizontal, the time when the aforementioned compound did not flow and gelled was visually judged as the "gelation time". The gelation inhibition was evaluated according to the following criteria. The results are presented in Table 2. Furthermore, since compound 1 did not gel even after being placed in the constant temperature bath for 180 minutes, its gelation time was set as "more than 180 minutes".

[0064] <Evaluation Criteria for Gelation Inhibition>

[0064] ◎:The gelation time is more than 120 minutes.

[0064] ○: Gelation time is between 60 and 110 minutes.

[0064] ×: Gelation time is less than 50 minutes.

[0065] [Table 2]

[0066] (Assessment of gelation inhibition 2)

[0066] The gelation inhibition of reaction solutions containing compounds 1 to 7 obtained in Examples 1 to 7 and compounds 8 to 10 obtained in Comparative Examples 1 to 3 was evaluated. Specifically, 2.85 g of any one of compounds 1 to 10, 0.15 g of polypropylene glycol dimethacrylate (average additional mole number of oxypropyl groups: 7), 3 mL of solvent (toluene), and 0.01 mole of polymerization initiator ("V-65", 2,2'-azobis(2,4-dimethylpentanones) manufactured by Fujifilm and Koimitsu Chemical Co., Ltd.) relative to 1 mole of polymerizable functional group (meth(acrylonitrile) group) were added to a capped test tube (10 mL) to prepare the reaction solution. The resulting reaction solution was bubbled with nitrogen, and the test tube was sealed with a cap. Then, the test tube containing the reaction solution was immersed in a constant temperature bath at 70°C and the test tube was shaken at a speed of 100 times per minute. After the test tubes were placed in the constant temperature bath, the state of the reaction solution in the test tubes was checked every 10 minutes (maximum: 180 minutes). When the test tubes were horizontal, the time it took for the reaction solution to stop flowing and gel was visually determined as the "gelation time". Gelation inhibition was evaluated according to the following criteria. The results are presented in Table 3. Furthermore, for reaction solutions that did not gel even after being placed in the constant temperature bath for up to 180 minutes, their gelation time was defined as "more than 180 minutes".

[0066] <Evaluation Criteria for Gelation Inhibition>

[0066] ◎:The gelation time is more than 120 minutes.

[0066] ○: Gelation time is between 60 and 110 minutes.

[0066] ×: Gelation time is less than 50 minutes.

[0067] [Table 3]

[0068] Example 8: Synthesis of Polymer 1

[0068] 10 g of compound 1 obtained in Example 1 and 0.01 mole of polymerization initiator ("V-65", 2,2'-azobis(2,4-dimethylpentanones) manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd.) relative to 1 mole of polymerizable functional group ((meth)acrylonitrile) were added to a petri dish. The mixture was stirred with a glass rod to prepare the mixture, and the resulting mixture was heated at 70°C for 3 hours under nitrogen atmosphere to synthesize polymer 1. The weight average molecular weight of polymer 1 was determined using the gel permeation chromatography apparatus described above.

[0069] Examples 9 to 14 and Comparative Examples 4 to 6: Synthesis of Polymers 2 to 10

[0069] Except for using any of the compounds 2 to 10 to replace compound 1, polymers 2 to 10 are synthesized in the same manner as polymer 1.

[0070] (Evaluation of strain resistance)

[0070] The strain resistance of polymers 1 to 10 obtained in Examples 8 to 14 and Comparative Examples 4 to 6 was evaluated using a viscoelasticity measuring apparatus MCR302 and a measuring probe (cone plate, PP25) (manufactured by Anton Pearl). Specifically, the storage modulus G' of the polymer was measured when the shear strain γ changed from 0.01 to 100 at 20°C. The shear strain γ when the storage modulus G' changed was taken as γmax, and the strain resistance was evaluated according to the following evaluation criteria. Since the shape or volume of the polymer changed due to the application of external force will return to its original state to γmax when the external force is removed, the larger the γmax, the better the strain resistance.

[0070] <Evaluation Criteria for Strain Resistance>

[0070] ◎:γmax is above 40

[0070] ○: γmax is above 30 but below 40

[0070] ×: γmax not reached 30

[0071] The compounds used in the synthesis of polymers 1 to 10, as well as the weight-average molecular weight, γmax and strain resistance of polymers 1 to 10, are presented in Table 4.

[0072] [Table 4]

[0073] Example 15 and Comparative Example 7: Manufacturing of Thin Film Composition

[0073] A composition for film preparation is prepared according to the mixing amounts shown in Table 5 below.

[0074] (Evaluation of viscosity inhibition of the composition)

[0074] The thickening inhibition of the film composition obtained in Example 15 and Comparative Example 7 was evaluated. Specifically, the aforementioned composition was placed in a constant temperature bath at 50°C under atmospheric conditions and heated for 2 hours. Using a RE-85 viscometer (Tokyo Machine Industry Co., Ltd.), the viscosity of the composition before heating (hereinafter referred to as "viscosity before heating") and the viscosity of the composition after heating (hereinafter referred to as "viscosity after heating") were measured at a temperature of 25°C and a rotor speed of 10 rpm, according to the following formula:

[0074] Vitality change rate = Viscosity after heating / Viscosity before heating

[0074] The viscosity change rate was measured. Furthermore, the viscosity-inhibiting effect of the components was evaluated according to the following criteria. The results are presented in Table 5.

[0074] <Evaluation Criteria for Inhibiting Thickening of Components>

[0074] ○: Viscosity change rate did not reach 1.10.

[0074] ×: Viscosity change rate is 1.10

[0075] [Table 5]

[0075] [Industrial Applicability]

[0076] According to the present invention, a polyalkylene glycol mono(meth)acrylate is provided, which can suppress gelation during polymer manufacturing. Polymers obtained from the polyalkylene glycol mono(meth)acrylate of the present invention are suitable as raw materials for coatings, etc. Furthermore, film compositions containing the polyalkylene glycol mono(meth)acrylate and polyfunctional (meth)acrylate monomers of the present invention are less prone to tackification during storage, and films obtained therefrom can be used for various applications.

[0077] This application is based on Japanese Patent Application No. 2020-19618, which was filed in Japan, and its contents are fully included in the description of this application.

Claims

1. A polyalkylene glycol mono(meth)acrylate, represented by the following formula (1), wherein the ratio wb / wf calculated from the chromatogram obtained by gel permeation chromatography satisfies the following relationship (2). CH2=CR-COO-(AO)nH In formula (1), R represents a hydrogen atom or a methyl group, AO represents at least one alkyl group with 2 to 4 carbon atoms, and when there are more than two AO groups, the additional form of (AO)n can be either block or random, and n represents the average additional mole number of the alkyl group, which is 5 to 100. 0.25≦wb / wf≦0.90 (2) In equation (2), when the holding time of the maximum peak height (h) in the aforementioned tomographic peaks is set as th, and two holding times of 1 / 10 of the maximum peak height (h1 / 10) are set as tf and tb, wf represents the difference between th and tf (th-tf), and wb represents the difference between tb and th (tb-th), but tf <tb。 2. The polyalkylene glycol mono(meth)acrylate as described in claim 1, wherein, In formula (1), AO is one or two of an oxoalkyl group with 2 or 3 carbon atoms.

3. A polymer obtained by polymerizing the polyalkylene glycol mono(meth)acrylate described in claim 1 or 2.

4. A film composition comprising component (A) and component (B), wherein, The content of component (A) relative to the total of components (A) and (B) is 20 to 50% by weight, and The content of component (B) is 50 to 80% by weight relative to the total of components (A) and (B): Ingredient (A): Polyalkylene glycol mono(meth)acrylate as described in claim 1 or 2, and Ingredient (B): Polyfunctional (meth)acrylate monomer.

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