Polyalkylene glycol mono(meth)acrylate and its polymer, and film composition

Abstract

A polyalkylene glycol mono(meth)acrylate which is represented by formula (1): CH2=CR-COO-(AO)n-H and in which the ratio wb / wf of wb and wf calculated from a chromatogram measured with gel permeation chromatography satisfies formula (2): 0.25 ≤ wb / wf ≤ 0.90 (the symbols in formulas (1) and (2) are defined in the specification), a polymer of the polyalkylene glycol mono(meth)acrylate, and also a film composition that contains said polyalkylene glycol mono(meth)acrylate are provided.

Description

[Technical field]

[0001] The present invention relates to a polyalkylene glycol mono(meth)acrylate and a polymer thereof, and a composition for film. Here, the term "composition for film" refers to a composition used to form a film. [Background technology]

[0002] Polyalkylene glycol mono(meth)acrylate (hereinafter sometimes referred to as "PAG mono(meth)acrylate") has a polymerizable functional group, and is therefore used as a raw material for acrylic resins, photocurable resins, etc. PAG mono(meth)acrylate is also used in a variety of applications, including photosensitive resins, coating materials, adhesives, binders, paints, inks, rubber, and thermoplastic elastomers.

[0003] It is also possible to modify the hydrophilic or hydrophobic nature of PAG mono(meth)acrylate by controlling the average number of moles added per mole of ethylene oxide (EO) or propylene oxide (PO) and the form of addition. In addition, by using PAG mono(meth)acrylate as a raw material for various materials, it is possible to impart flexibility, elasticity, strain resistance, and adhesion to each material.

[0004] For example, conventional acrylic resins used in films have the drawback of low flexibility, but flexible films can be formed from compositions containing PAG mono(meth)acrylates.

[0005] Various techniques have been developed for PAG mono(meth)acrylate. For example, Patent Document 1 describes a method for producing polyethylene glycol monoacrylate, which is characterized by using a boron trifluoride compound as a catalyst, ring-opening polymerizing 2-hydroxyethyl acrylate with ethylene oxide, adding an adsorbent for removing the boron trifluoride compound, and treating at 0 to 50°C.

[0006] In addition, Patent Document 2 discloses a compound represented by the following formula (I): CH2=C(R 1 )-COO-(R 2 O) n -H (I) (Each symbol in formula (I) is as described in Patent Document 2.) and polymerizing the resulting (meth)acrylate. In addition, the above formula (I) is described as "formula (1)" in Patent Document 2. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2005-281274 A [Patent Document 2] JP 2006-070147 A Summary of the Invention [Problem to be solved by the invention]

[0008] The polymers obtained by polymerizing conventional PAG mono(meth)acrylates have insufficient performance (e.g., strain resistance). Furthermore, in the production of polymers by polymerizing conventional PAG mono(meth)acrylates, gelation of the product occurs, leading to deterioration of the product's quality and function, as well as reduced productivity.

[0009] Furthermore, in order to increase the hardness of the resulting film, a large amount of a polyfunctional monomer may be blended into the film composition. In the production of a film using a film composition containing a polyfunctional monomer, a thin film is formed from the film composition, and then the thin film is cured. If the film composition thickens during storage, it is necessary to change the conditions during film production (particularly, during thin film formation). Therefore, there is a demand for a film composition that is less likely to thicken during storage.

[0010] An object of the present invention is to provide a polyalkylene glycol mono(meth)acrylate capable of suppressing gelation during the production of a polymer. Another object of the present invention is to provide a polyalkylene glycol mono(meth)acrylate capable of producing a polymer having excellent strain resistance. Still another object of the present invention is to provide a film composition which is less likely to thicken during storage. [Means for solving the problem]

[0011] As a result of intensive research in light of the above matters, the present inventors have found that the above-mentioned problems can be solved by a polyalkylene glycol mono(meth)acrylate and a polymer thereof, which have an asymmetric elution peak in a chromatogram obtained by gel permeation chromatography measurement and a molecular weight distribution biased toward the high molecular weight side, and a film composition containing the polyalkylene glycol mono(meth)acrylate.

[0012] That is, the present invention is as follows. [1] Formula (1): CH2=CR-COO-(AO) n -H (1) 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, and when two or more AO are present, (AO) n The addition form of may be either block or random, and n represents the average number of moles of oxyalkylene groups added and is a number from 5 to 100. and is calculated from a chromatogram obtained by gel permeation chromatography measurement. b And w f The ratio of b / w f But equation (2): 0.25≦w b / w f ≦0.90 (2) (In formula (2), the retention time at the maximum peak height (h) in the chromatogram peak is t h and 1 / 10 of the maximum peak height (h 1 / 10 ) two retention times at t f and t b (However, t f <t b ), then w f is h and f Difference from (t h -t f ), and w b is b and h Difference from (t b -t h ) is shown. A polyalkylene glycol mono(meth)acrylate which satisfies the above relationship. [2] The polyalkylene glycol mono(meth)acrylate according to the above [1], wherein AO in the formula (1) is one or two kinds of oxyalkylene groups having 2 or 3 carbon atoms. [3] A polymer obtained by polymerizing the polyalkylene glycol mono(meth)acrylate according to [1] or [2] above. [4] A composition for a film comprising the following components (A) and (B): The content of component (A) is 20 to 50% by weight based on the total of components (A) and (B); and A composition for film, in which the content of component (B) is 50 to 80% by weight based on the total of components (A) and (B): (Component (A)) the polyalkylene glycol mono(meth)acrylate described in [1] or [2] above, and (Component (B)) A polyfunctional (meth)acrylate monomer. Effect of the Invention

[0013] The polyalkylene glycol mono(meth)acrylate of the present invention has an excellent effect of suppressing gelation during the production of a polymer. Furthermore, 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, etc.

[0014] Furthermore, the film-forming composition containing the polyalkylene glycol mono(meth)acrylate and the polyfunctional (meth)acrylate monomer of the present invention is less likely to thicken during storage. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 is a model of a chromatogram obtained by gel permeation chromatography measurement of a polyalkylene glycol mono(meth)acrylate, for explaining wf and wb. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] In this specification, a numerical range defined using the symbol "~" is intended to include both the upper and lower limits of the range. For example, "2~4" means 2 or more and 4 or less. In this specification, "(meth)acrylate" refers to acrylate or methacrylate. Here, the (meth)acrylate may be used alone or in combination of two or more kinds. The term "(meth)acryloyl group" and the like also have the same meaning as "(meth)acrylate".

[0017] <PAGモノ(メタ)アクリレート> The PAG mono(meth)acrylates of the present invention have the formula (1): CH2=CR-COO-(AO) n -H (1) 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, and when two or more AO are present, (AO) nThe additional form may be either block or random, and n represents the average number of moles of oxyalkylene groups added, which is a number from 5 to 100. ) It is a compound represented by

[0018] AO is at least one kind of oxyalkylene group having 2 to 4 carbon atoms. That is, AO is at least one kind selected from the group consisting of an oxyethylene group, an oxypropylene group, and an oxybutylene group. AO is preferably one or two kinds of oxyalkylene groups having 2 or 3 carbon atoms, and more preferably an oxypropylene group. n is the average number of moles of oxyalkylene groups added. Therefore, n may be 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.

[0019] <Properties of PAG mono(meth)acrylate in gel permeation chromatography analysis> The PAG mono(meth)acrylate of the present invention is calculated from a chromatogram (vertical axis: refractive index intensity, horizontal axis: retention time) obtained by gel permeation chromatography (GPC) measurement using a differential refractometer, w b and w f The ratio w b / w f is given by the formula (2): 0.25 ≦ w b / w f ≦ 0.90 (2) (In formula (2), at the peak of the chromatogram, the retention time at the maximum peak height (h) is t h , and the two retention times at 1 / 10 of the maximum peak height (h 1 / 10 ) are t f and t b (provided that t f < t b ). In this case, w f is the difference (t h - t f ) between t h and t f , and w b is the difference (t b - t h ) between tb -t h ) is shown. The above relationship is satisfied (see FIG. 1).

[0020] w b / w f When w is smaller than 0.25, the molecular weight distribution of the PAG mono(meth)acrylate is biased toward the high molecular weight side, the concentration of the polymerizable functional group is decreased, and the polymerization property of the PAG mono(meth)acrylate may decrease. b / w f is preferably 0.30 or more, and more preferably 0.35 or more.

[0021] On the other hand, w b / w f When w is greater than 0.90, the PAG mono(meth)acrylate of the present invention itself and the reaction solution containing the PAG mono(meth)acrylate of the present invention are likely to gel. b / w f When w is greater than 0.90, the polymer obtained by polymerizing the PAG mono(meth)acrylate of the present invention has insufficient strain resistance. Here, "strain resistance" refers to the property of returning the shape or volume of an object that has changed due to the application of an external force to the object to its original state when the external force is removed. From the viewpoint of gelation inhibition and strain resistance, b / w f is preferably 0.80 or less, and more preferably 0.60 or less.

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

[0023] <Production of PAG mono(meth)acrylate> The PAG mono(meth)acrylate of the present invention can be produced by adding ethylene oxide, propylene oxide, butylene oxide (preferably propylene oxide) to a starting material (for example, 2-hydroxypropyl methacrylate) in the presence of a double metal cyanide complex catalyst (hereinafter sometimes abbreviated as "DMC catalyst"). Specifically, the starting material and the DMC catalyst are added into a reaction vessel, and ethylene oxide, propylene oxide, butylene oxide (hereinafter collectively referred to as "alkylene oxides having 2 to 4 carbon atoms") are continuously or intermittently added and subjected to addition polymerization under stirring in an inert gas atmosphere. The alkylene oxides having 2 to 4 carbon atoms may be added under pressure or added at atmospheric pressure.

[0024] Average supply rate of alkylene oxides having 2 to 4 carbon atoms teeth is changed according to the charged amount of the alkylene oxides having 2 to 4 carbon atoms do.Specifically, when V1 is the rate during which 5% by weight or more and 20% by weight or less of the total amount of alkylene oxide having 2 to 4 carbon atoms is supplied (amount supplied per unit time), V2 is the rate during which more than 20% by weight and 50% by weight or less of the total amount of alkylene oxide having 2 to 4 carbon atoms is supplied, and V3 is the rate during which more than 50% by weight and 100% by weight or less of the total amount of alkylene oxide having 2 to 4 carbon atoms is supplied, in one embodiment for producing a PAG mono(meth)acrylate of the present invention, the average supply rate of the alkylene oxide having 2 to 4 carbon atoms is controlled so that V1 / V2=1.1 to 2.0 and V2 / V3=1.1 to 1.5. do. In another embodiment of the method for producing the PAG mono(meth)acrylate of the present invention, the average supply rate of the alkylene oxide having 2 to 4 carbon atoms is controlled so that V1 / V2=0.4 to 0.9 and V2 / V3=0.5 to 0.95. do.

[0025] The reaction temperature for adding an alkylene oxide having 2 to 4 carbon atoms to the starting material is preferably 50° C. to 120° C., and more preferably 70° C. to 90° C. If the reaction temperature is lower than 50° C., the reaction rate is very slow, and if it is higher than 120° C., problems such as polymerization of the polymerizable groups in the starting material and coloring occur.

[0026] There are no particular limitations on the trace amounts of water contained in the starting materials and the alkylene oxide having 2 to 4 carbon atoms, but it is desirable that the amount of water contained in the starting materials is 0.5% by weight or less, and the amount of water contained in the alkylene oxide having 2 to 4 carbon atoms is 0.01% by weight or less.

[0027] The amount of the DMC catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, based on 100 parts by weight of the alkylene oxide derivative produced. The DMC catalyst may be added to the reaction system all at once at the beginning, or may be added in portions one by one. After the polymerization reaction is completed, the DMC catalyst is removed. The catalyst can be removed by a known method such as filtration, centrifugation, or treatment with a synthetic adsorbent.

[0028] In the production of PAG mono(meth)acrylate, a known DMC catalyst can be used. The DMC catalyst is, for example, a catalyst represented by the formula (3): M a [M' x (CN) y ] b (H2O) c (L) d (3) (In formula (3), M and M' represent metal atoms, L represents an organic ligand, and a, b, c, d, x, and y represent positive integers.) It is possible to use those represented by the following formula:

[0029] Examples of the metal atom (metal cation) 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. Of these, Zn(II) is preferably used.

[0030] Examples of the metal atom (metal cation) 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 preferably used.

[0031] As the organic ligand L, for example, alcohol, ether, ketone, ester, etc. can be used, and alcohol is more preferable. Preferred organic ligands are water-soluble, and specific examples include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, N,N-dimethylacetamide, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), etc. A particularly preferred DMC catalyst is Zn(II)3[Co(III)(CN)6]2(H2O)4(tert-butyl alcohol)2 coordinated with tert-butyl alcohol.

[0032] In the reaction of adding an alkylene oxide having 2 to 4 carbon atoms to the starting material, other additives may be used within the range that does not impair the characteristics of the present invention. For example, hydroquinone (HQ), hydroquinone monomethyl ether (MQ), 2,6-di-tert-butylhydroxytoluene (BHT), di-tert-butylhydroxyanisole (BHA), α-tocopherol, β-tocopherol, γ-tocopherol, etc. can be added to the reaction system as a polymerization inhibitor. The polymerization inhibitor is preferably MQ and / or BHT, more preferably BHT. The amount of the polymerization inhibitor to be added is preferably 0.001 to 0.3 parts by weight per 100 parts by weight of the total of the starting material (e.g., 2-hydroxypropyl methacrylate) and the alkylene oxide having 2 to 4 carbon atoms. If the amount of addition is less than 0.001 part by weight, the function of the polymerization inhibitor becomes insufficient, and gelation may occur during the addition of the alkylene oxide having 2 to 4 carbon atoms. On the other hand, if the amount added is more than 0.3 parts by weight, the purity of the resulting PAG mono(meth)acrylate may decrease.

[0033] <Polymer> The present 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 may be obtained by copolymerizing PAG mono(meth)acrylate with other polymerizable compounds. Examples of other polymerizable compounds include (meth)acrylic acid esters without PAG chains, such as methyl acrylate and methyl methacrylate, acrylonitrile, methacrylonitrile, styrene, butadiene, etc. The amount of PAG mono(meth)acrylate used during polymerization varies depending on the application, but is preferably 10% by weight or more, more preferably 20% by weight or more, even more preferably 30% by weight or more, and particularly preferably 50% by weight or more and 100% by weight or less, based on the total amount of PAG mono(meth)acrylate and other polymerizable compounds.

[0034] The polymerization method for obtaining the polymer of the present invention may be appropriately selected from solution polymerization, emulsion polymerization, bulk polymerization, and the like. The polymerization may be carried out by a known method (for example, thermal polymerization, photopolymerization, electron beam polymerization). To obtain the polymer of the present invention, it is preferable to use a polymerization initiator (thermal polymerization initiator or photopolymerization initiator). The polymerization initiator may be used alone or in combination of two or more kinds.

[0035] Examples of the thermal polymerization initiator include t-butyl peroxypivalate, t-hexyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-bis(t-butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)valerate, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and di-t-butyl peroxide. Organic peroxides such as t-butyl cumyl peroxide, dicumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, benzoyl peroxide, and t-butylperoxyisopropyl carbonate, as well as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 1,1'-azobis(2,4-dimethylvaleronitrile). Bis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine] dihydrochloride, 2,2'-azobis[N-hydroxyphenyl]-2-methylpropionamidine] dihydrochloride, 2,2'-azobis[2-methyl-N-(phenylmethyl)propionamidine] dihydrochloride, 2,2'-azobis[2-methyl-N-(phenylmethyl)propionamidine] dihydrochloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propionamidine] dihydrochloride, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-hydroxyethyl)-2-methylpropionamidine] 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-diazepin-2-yl)propane] dihydrochloride, 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]propionamide}, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], Examples of azo compounds include 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis[2-(hydroxymethyl)propionitrile].

[0036] Thermal polymerization using a thermal polymerization initiator can be carried out at a temperature range and for a polymerization time that is usually used. The amount of the thermal polymerization initiator used is usually 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, per mol of the polymerizable functional group ((meth)acryloyl group).

[0037] Examples of the photopolymerization initiator include 1-hydroxycyclohexan-1-yl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-1-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanoic acid. acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and aromatic peroxy acid ester compounds such as 1,3-di(t-butyldioxycarbonyl)benzene and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone.

[0038] Photopolymerization can be carried out in the wavelength range and irradiation time of light that is usually used. The amount of photopolymerization initiator used is usually 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, per mol of polymerizable functional group (meth(acryloyl) group). In photopolymerization, sensitization using a dye may be carried out.

[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 further preferably 5,000 to 3,000,000. The weight average molecular weight is a value measured by gel permeation chromatography under the above-mentioned conditions.

[0040] <Film Composition> The present invention provides a composition for a film comprising the following components (A) and (B): The content of component (A) is 20 to 50% by weight based on the total of components (A) and (B); and A film composition is provided, in which the content of component (B) is 50 to 80% by weight based on the total content of components (A) and (B): (Component (A)) a PAG mono(meth)acrylate of the present invention that meets the above requirements, and (Component (B)) A polyfunctional (meth)acrylate monomer.

[0041] <Component (A)> The component (A) of the film composition of the present invention is the PAG mono(meth)acrylate of the present invention. The PAG mono(meth)acrylate of the present invention is as described above. The PAG mono(meth)acrylate of the present invention may be used alone or in combination of two or more kinds.

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

[0043] <Ingredient (B)> The component (B) of the film composition of the present invention is a polyfunctional (meth)acrylate monomer, which improves the curing property of the film composition. Here, the term "polyfunctional (meth)acrylate" means a (meth)acrylate having two or more (meth)acryloyl groups in one molecule. In addition, the term "bifunctional (meth)acrylate" described later means a (meth)acrylate having two (meth)acryloyl groups in one molecule. The term "trifunctional (meth)acrylate" and the like also have the same meaning as "bifunctional (meth)acrylate".

[0044] Component (B) may be used alone or in combination of two or more. Examples of component (B) include alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate; polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(meth)acrylate; neopentyl glycol di(meth)acrylate, tricyclo Bifunctional (meth)acrylates other than alkylene glycol di(meth)acrylates and polyalkylene glycol di(meth)acrylates, such as decanedimethanol di(meth)acrylate, polycarbonate diol di(meth)acrylate, polyester diol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, and polyurethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone modified tris(meth)acrylate, R Examples of the functional (meth)acrylate include trifunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, tetrafunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, pentafunctional (meth)acrylates such as dipentaerythritol penta(meth)acrylate, and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate. Among these, alkylene glycol di(meth)acrylates are preferred, and butylene glycol di(meth)acrylate is more preferred.

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

[0046] <Polymerization initiator> The film composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be used alone or in combination of two or more. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator. The thermal polymerization initiator and the photopolymerization initiator may be used alone or in combination of two or more. Examples of the thermal polymerization initiator and the photopolymerization initiator include those mentioned 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, per 1 mol of the polymerizable functional group ((meth)acryloyl group) in the film composition of the present invention.

[0048] <Monofunctional (meth)acrylate monomer> From the viewpoint of suppressing thickening, the film-forming composition of the present invention preferably contains a monofunctional (meth)acrylate monomer other than polyalkylene glycol mono(meth)acrylate.

[0049] The monofunctional (meth)acrylate monomer may be used alone or in combination of two or more. Examples of the monofunctional (meth)acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, and 1-adamantyl (meth)acrylate. Among these, methyl (meth)acrylate is preferred.

[0050] When a monofunctional (meth)acrylate monomer is used, the content thereof is preferably 10 to 40 parts by weight, more preferably 15 to 40 parts by weight, and further preferably 20 to 40 parts by weight, based on 100 parts by weight of component (B).

[0051] <Other ingredients> The film composition of the present invention may contain other components different from the above-mentioned component (A), component (B), polymerization initiator, and monofunctional (meth)acrylate within the range that does not impair the effects of the present invention. Examples of other components include carboxyl group-containing resins, (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, phenolic novolac resins, cresol novolac resins, antistatic agents, antioxidants, rubber, silica particles, zirconia, plasticizers, ultraviolet absorbers, defoamers, thixotropic agents, release agents, fillers, fluorescent materials, pigments, etc. The other components may be used alone or in combination of two or more.

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

[0053] <Film Uses> Applications of the films obtained from the film composition of the present invention include, for example, components for light-emitting diode modules, mobile phones, smartphones, tablet terminals, personal computers, cameras, organic electroluminescence (organic EL) devices, flat panel displays, touch panels, electronic paper, photodiodes, phototransistors, solar cells, dry film resists, projectors, home appliances, automobiles, motorcycles, heavy machinery, railway vehicles, ships, building materials, smoke-proof vertical walls, smoke-proof curtains, decorative panels, and the like. EXAMPLES

[0054] The present invention will be described in detail below with reference to examples.

[0055] Synthesis example 1: Synthesis of double metal cyanide complex (DMC) catalyst Into 2.0 mL of an aqueous solution containing 2.1 g of zinc chloride, 15 mL of an aqueous solution containing 0.84 g of potassium hexacyanocobaltate K3Co(CN)6 was added dropwise over 15 minutes while stirring at 40°C. After the addition was completed, 16 mL of water and 16 g of tert-butyl alcohol were added, the temperature was raised to 70°C, and the mixture was stirred for 1 hour. After cooling to room temperature, a filtration operation (first time) was performed to obtain a solid. To this solid, 14 mL of water and 8.0 g of tert-butyl alcohol were added, and the mixture was stirred for 30 minutes, and a filtration operation (second time) was performed to obtain a solid.

[0056] To the obtained solid, 18.6 g of tert-butyl alcohol and 1.2 g of methanol were added and stirred for 30 minutes. After that, a filtration operation (third time) was performed, and the obtained solid was dried at 40 °C under reduced pressure for 3 hours to obtain 0.7 g of DMC catalyst (Zn (II) 3 [Co (III) (CN) 6] 2 (H 2 O) 4 (tert-butyl alcohol) 2).

[0057] Example 1: Synthesis of Compound 1 500 g of 2-hydroxypropyl methacrylate (water content 0.02 wt%), 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 charged into a stainless steel 5-liter (capacity 4,890 mL) pressure-resistant reactor equipped with a thermometer, a pressure gauge, a safety valve, a nitrogen gas inlet tube, a stirrer, a vacuum exhaust tube, a cooling coil, and a steam jacket. After nitrogen replacement, the temperature was raised to 70°C, and 403 g of propylene oxide (methyloxirane, water content 0.005 wt%) was added dropwise from the nitrogen gas inlet tube while stirring under conditions of 0.3 MPa or less. The pressure and temperature in the reactor were observed over time, and the pressure in the reactor was suddenly reduced 5 hours after the end of the dropwise addition of 403 g of propylene oxide. Thereafter, while maintaining the inside of the reaction tank at 70°C, 1132g of propylene oxide was gradually dropped from the nitrogen gas inlet tube under the condition of 0.5MPa or less. The average supply rates were V1 260g / hour, V2 203g / hour, and V3 152g / hour (V1 / V2=1.28, V2 / V3=1.34). After the dropwise addition, the reaction was allowed to proceed at 70°C for 0.5 hours, and then the reaction mixture was extracted from the reaction layer, and the reaction mixture was filtered to remove solids, thereby obtaining liquid compound 1. The obtained compound 1 was subjected to gel permeation chromatography measurement using the above-mentioned HLC-8320GPC (registered trademark).

[0058] Examples 2 to 4: Synthesis of Compounds 2 to 4 Compounds 2 to 4 were synthesized in the same manner as in the synthesis of compound 1, except for the number of moles of propylene oxide added, or the number of moles of propylene oxide added and the starting material. The obtained compounds 2 to 4 were measured by gel permeation chromatography in the same manner as above.

[0059] Examples 5 to 8: Synthesis of Compounds 5 to 7 Compounds 5 to 7 were synthesized in the same manner as in the synthesis of compound 1, except that ethylene oxide and propylene oxide or 1,2-butylene oxide were used as the alkylene oxide instead of propylene oxide, the number of moles of alkylene oxide added was changed, and the starting materials were those shown in Table 1 below. The obtained compounds 5 to 7 were measured by gel permeation chromatography in the same manner as above. 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 obtain (AO) n Compound 5 was synthesized in which the addition form of was random. In Example 6, propylene oxide was first added to the starting material, and then ethylene oxide was added to obtain (AO) n Compound 6, in which the addition form is blocked, was synthesized.

[0060] Comparative Example 1: Synthesis of Compound 8 500 g of 2-hydroxypropyl methacrylate, 17.6 g of boron trifluoride diethyl ether complex, and 0.6 g of hydroquinone monomethyl ether (MQ) were charged into a stainless steel 5-liter (capacity 4,890 mL) pressure-resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen gas inlet tube, stirrer, vacuum exhaust tube, cooling coil, and steam jacket. After nitrogen replacement, the temperature was raised to 60°C, and 1578 g of propylene oxide (methyloxirane) was added dropwise from the nitrogen gas inlet tube under conditions of 0.3 MPa or less while stirring. After the dropwise addition, the reaction was carried out at 60°C for 0.5 hours, and after adding water and hexane, the mixture was neutralized with an aqueous sodium hydroxide solution. After removing the aqueous layer, the hexane and water were distilled off under reduced pressure, and the concentrate was filtered to remove solids, and the liquid compound was obtained. 8 The obtained compound 8 was subjected to measurement by gel permeation chromatography in the same manner as described above.

[0061] Comparative Examples 2 and 3: Synthesis of Compounds 9 and 10 Compounds 9 and 10 were synthesized in the same manner as in the synthesis of compound 8, except for the number of moles of propylene oxide added, or the number of moles of propylene oxide added and the starting material. 9 and 10 was measured by gel permeation chromatography in the same manner as above.

[0062] Starting materials used in the synthesis of compounds 1 to 10, and the w calculated from the chromatographs obtained for compounds 1 to 10 b / w f Furthermore, the properties of compounds 1 to 10 are shown in Table 1. However, the molecular weight is calculated from the hydroxyl value measured in accordance with JIS K-1557-1j.

[0063] [Table 1]

[0064] (Gelling Inhibition Evaluation 1) The gelation inhibition of compound 1 obtained in Example 1 and compound 8 obtained in Comparative Example 1 was evaluated. Specifically, 15 g of the compound was weighed in a screw tube (30 mL), and the screw tube containing the compound was placed in a thermostatic bath at 150° C. under a nitrogen atmosphere, and the time from the placement of the screw tube in the thermostatic bath until the compound gelled (gelation time) was measured. After the screw tube was placed in the thermostatic bath, the state of the compound in the screw tube was confirmed every 10 minutes (maximum: 180 minutes), and the time when the compound did not flow and was visually judged to have gelled when the screw tube was placed horizontally was taken as the "gelation time", and the gelation inhibition was evaluated according to the following criteria. The results are shown in Table 2. Compound 1 did not gel even after 180 minutes from the placement of the screw tube in the thermostatic bath, so its gelation time was taken as "180 minutes or more". <Evaluation Criteria for Gelation Inhibition> ◎: Gelling time is 120 minutes or more ○: Gelling time is 60 minutes or more and 110 minutes or less ×: gelation time is 50 minutes or less

[0065] [Table 2]

[0066] (Gelling Inhibition Evaluation 2) The gelation inhibition of the reaction solution containing the compounds 1 to 7 obtained in Examples 1 to 7 or the compounds 8 to 10 obtained in Comparative Examples 1 to 3 was evaluated. Specifically, 2.85 g of any of the compounds 1 to 10, 0.15 g of polypropylene glycol dimethacrylate (average number of moles of oxypropylene groups added: 7), 3 mL of solvent (toluene), and 0.01 mole of polymerization initiator ("V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 2,2'-azobis(2,4-dimethylvaleronitrile)) per mole of polymerizable functional group (meth(acryloyl) group) were added to a capped test tube (10 mL) to prepare a reaction solution, and the reaction solution was bubbled with nitrogen and the test tube was sealed with a cap. Thereafter, the test tube containing the reaction solution was immersed in a thermostatic bath at 70°C, and the test tube was shaken at a speed of 100 times / min. After the test tube was placed in the thermostatic bath, the state of the reaction solution in the test tube was checked every 10 minutes (maximum: 180 minutes), and the time when it was visually determined that the reaction solution did not flow and gelled when the test tube was placed horizontally was taken as the "gelling time", and gelling inhibition was evaluated according to the following criteria. The results are shown in Table 3. Note that if the reaction solution did not gel even after 180 minutes from the time the test tube was placed in the thermostatic bath, the gelling time was rated as "180 minutes or more." <Evaluation Criteria for Gelation Inhibition> ◎: Gelling time is 120 minutes or more ○: Gelling time is 60 minutes or more and 110 minutes or less ×: gelation time is 50 minutes or less

[0067] [Table 3]

[0068] Example 8: Synthesis of Polymer 1 10 g of the compound 1 obtained in Example 1 and a polymerization initiator (FUJIFILM Wako Pure Chemical Industries, Ltd. "V-65", 2,2'-azobis(2,4-dimethylvaleronitrile)) were added to a petri dish in an amount of 0.01 mol per mol of the polymerizable functional group ((meth)acryloyl group), and the mixture was stirred with a glass stirring rod to prepare a mixture. The resulting mixture was heated at 70°C for 3 hours in a nitrogen atmosphere to synthesize polymer 1. The weight average molecular weight of the obtained polymer 1 was measured by the above-mentioned gel permeation chromatography.

[0069] Examples 9 to 14 and Comparative Examples 4 to 6: Synthesis of Polymers 2 to 10 Polymers 2 to 10 were synthesized in the same manner as in the synthesis of Polymer 1, except that compound 1 was replaced with any of compounds 2 to 10.

[0070] (Evaluation of strain resistance) 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 device MCR302 and a measuring probe (cone plate, PP25) (manufactured by Anton Paar). Specifically, the storage modulus G' was measured when the shear strain γ of the polymer at 20°C was changed from 0.01 to 100. The shear strain γ when the storage modulus G' was changed was expressed as γ max The strain resistance was evaluated according to the following evaluation criteria. The shape and volume of the polymer changed due to an external force applied to it when the external force was removed were γ max Since the return to normal is max The larger the value, the better the strain resistance. <Evaluation criteria for strain resistance> ◎:γ max is 40 or more 〇:γ max is between 30 and 40 ×:γ max is less than 30

[0071] Compounds used in the synthesis of polymers 1 to 10, and weight average molecular weights and γ max The evaluation results of the strain resistance and the strength are shown in Table 4.

[0072] [Table 4]

[0073] Example 15 and Comparative Example 7: Preparation of film composition A film composition was prepared using the blending amounts shown in Table 5 below.

[0074] (Evaluation of Inhibition of Thickening of Composition) The film-forming compositions obtained in Example 15 and Comparative Example 7 were evaluated for their inhibition of thickening. Specifically, the compositions were placed in a thermostatic chamber at 50° C. in an air atmosphere and heated for 2 hours. 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 using an RE-85 viscometer (Toki Sangyo Co., Ltd.) at a temperature of 25° C. and a rotor rotation speed of 20 rpm, and calculated using the following formula: Viscosity change rate = Viscosity after heating / Viscosity before heating The viscosity change rate was measured. The inhibition of thickening of the composition was evaluated according to the following criteria. The results are shown in Table 5. <Evaluation Criteria for Suppression of Viscosity Increase in Composition> ○: Viscosity change rate is less than 1.10 ×: Viscosity change rate is 1.10 or more

[0075] [Table 5] [Industrial Applicability]

[0076] According to the present invention, it is possible to provide a polyalkylene glycol mono(meth)acrylate capable of suppressing gelation during the production of a polymer. The polymer obtained from the polyalkylene glycol mono(meth)acrylate of the present invention is suitable as a raw material for coating films, etc. In addition, the film composition containing the polyalkylene glycol mono(meth)acrylate of the present invention and a polyfunctional (meth)acrylate monomer is unlikely to thicken during storage, and the film obtained therefrom can be used for various purposes.

[0077] This application is based on Patent Application No. 2020-19618 filed in Japan, the contents of which are incorporated in their entirety herein. [Explanation of symbols]

[0078] h Maximum peak height h 1 / 10 1 / 10 of maximum peak height t h Retention time at maximum peak height (h) t f 1 / 10 of the maximum peak height (h 1 / 10 ) retention time (where t f <t b ) t b 1 / 10 of the maximum peak height (h 1 / 10 ) retention time (where t f <t b ) w f t h and f Difference from (t h -t f ) w b t b and h Difference from (t b -t h )

Claims

1. Formula (1): CH ２ =CR-COO-(AO) ｎ -H (1) 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, and when two or more types of AO are present, (AO) ｎ The addition form of may be either block or random, and n represents the average number of moles of oxyalkylene groups added and is a number from 5 to 100. and is calculated from a chromatogram obtained by gel permeation chromatography measurement. ｂ And w ｆ The ratio of ｂ / w ｆ But, formula (2): 0.25≦w ｂ / w ｆ ≦0.90 (2) (In formula (2), the retention time at the maximum peak height (h) in the peak of the chromatogram is t ｈ The height of the maximum peak is 1 / 10 of the maximum peak height (h １／１０ ) two retention times at t ｆ and t ｂ (However, t ｆ <t ｂ ), then w ｆ is ｈ and ｆ The difference between (t ｈ -t ｆ ), and w ｂ is ｂ and ｈ The difference between (t ｂ -t ｈ ) is shown. A polyalkylene glycol mono(meth)acrylate which satisfies the above relationship.

2. 2. The polyalkylene glycol mono(meth)acrylate according to claim 1, wherein AO in formula (1) is one or two oxyalkylene groups having 2 or 3 carbon atoms.

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

4. A composition for a film comprising the following components (A) and (B): The content of component (A) is 20 to 50% by weight based on the total of components (A) and (B); and A film-forming composition in which the content of component (B) is 50 to 80% by weight based on the total of components (A) and (B): (Component (A)) The polyalkylene glycol mono(meth)acrylate according to claim 1 or 2, and (Component (B)) A polyfunctional (meth)acrylate monomer.

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