TW202136199A - Polyalkylene glycol mono (meth) acrylate and polymer thereof, and film composition - Google Patents

Abstract

The present invention provides a polyalkylene glycol mono (meth) acrylate which is represented by the formula (1): CH₂ = CR-COO-(AO)_n-H, 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

Description

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

The present invention relates to polyalkylene glycol mono(meth)acrylates and their polymers, as well as compositions for films. Here, "composition for thin film" refers to a composition that can be used to form a thin film.

Polyalkylene glycol mono(meth)acrylate (hereinafter also referred to as "PAG mono(meth)acrylate") has a polymerizable functional group, so it can be used as a raw material such as acrylic resin or photocurable resin. In addition, PAG mono(meth)acrylate can be used in various applications such as photosensitive resins, coating materials, adhesives, binders, coatings, inks, rubbers, and thermoplastic elastomers.

The hydrophilicity or hydrophobicity of PAG mono(meth)acrylate can be improved by controlling the average number of additional moles per mole equivalent of ethylene oxide (EO) or propylene oxide (PO) or the additional form. In addition, by using PAG mono(meth)acrylate as a raw material of various materials, it is possible to impart flexibility, flexibility, elasticity, strain resistance, and adhesion to various materials.

For example, conventional acrylic resins that can be used on films have the disadvantage of low flexibility. However, the PAG mono(meth)acrylate-containing composition can form a flexible film.

Regarding PAG mono(meth)acrylate, various technologies have been developed so far. For example, the method for producing polyalkylene glycol mono(meth)acrylate described in Patent Document 1 uses a boron trifluoride compound as a catalyst to open ethylene oxide in 2-hydroxyethyl acrylate. After the ring polymerization, an adsorbent for removing the boron trifluoride compound is added and treated at 0 to 50°C.

In addition, the method for producing a polymer described in Patent Document 2 is to synthesize (meth)propionic acid represented by the following formula (I) by reacting (meth)acrylic acid and alkylene oxide in the presence of a catalyst ester,

CH ₂ =C(R ¹ )-COO-(R ² O) _n -H (I)

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

A method of polymerizing the obtained (meth)propionate to produce a polymer. In addition, the above-mentioned formula (I) is described in Patent Document 2 as "formula (1)".

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-281274

[Patent Document 2] JP 2006-070147 A

The polymer obtained by polymerizing the conventional PAG mono(meth)acrylate has insufficient performance (for example, strain resistance). In addition, in the production of polymers by polymerizing conventional PAG mono(meth)acrylates, gelation of the products occurs, so that the quality and functions of the products are lowered, and the yield is lowered.

In addition, in order to increase the hardness of the resulting film, a large amount of multifunctional monomers can be blended in the film composition. In the production of a film using a composition for a film containing a polyfunctional monomer, after the film is formed from the composition for a film, the film is cured. When the aforementioned film composition increases viscosity during storage, it is necessary to change the conditions at the time of film production (especially, when the film is formed). Therefore, a film composition that is difficult to increase in viscosity during storage is required.

The object of the present invention is to provide a polyalkylene glycol mono(meth)acrylate which can suppress gelation during polymer production. In addition, the object of the present invention is to provide a polyalkylene glycol mono(meth)acrylate, which can obtain a polymer with excellent strain resistance. In addition, another object of the present invention is to provide a composition for a film that is difficult to increase in viscosity during storage.

As a result of intensive research in view of the above matters, the inventors found a polyalkylene glycol mono(meth)acrylate and its polymer, and a composition for films containing the aforementioned polyalkylene glycol mono(meth)acrylate Things, and solve the above problems. The elution peak system of the polyalkylene glycol mono(meth)acrylate in the chromatogram obtained by the gel permeation chromatography measurement is asymmetric, and the molecular weight distribution is biased toward the high molecular weight side.

That is, the present invention is as follows.

[1] A polyalkylene glycol mono(meth)acrylate, represented by the following formula (1), and w _b and w _{f calculated from a chromatogram obtained by a gel permeation chromatography measurement} The ratio w _b /w _f satisfies the relationship of the following formula (1),

CH ₂ =CR-COO-(AO) _n -H

(In formula (1), R represents a hydrogen atom or a methyl group, and AO represents at least one of the oxyalkylene groups having 2 to 4 carbon atoms. When there are more than two types of AO, the additional form of _{(AO) n can be} Either block or random, and n represents the average number of additional moles of oxyalkylene groups, which is 5 to 100.)

0.25≦w _b /w _f ≦0.90 (2)

(In formula (2), among the peaks of the aforementioned chromatogram, the retention time in the maximum peak height (h) is set to be t _h and 1/10 of the maximum peak height (h _1/10 ). When set to t _f and t _b (but, t _f <t _b ), w _f represents the difference between t _{h and t f (t h} -t _f ), and w _b represents the difference between t _{b and t h (t b} -t _h ).)

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

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

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

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

The content of component (B) is 50 to 80% by weight relative to the total of component (A) and component (B),

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

Component (B): Multifunctional (meth)acrylate monomer.

The polyalkylene glycol mono(meth)acrylate of the present invention has an excellent effect of inhibiting 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 monomers of the present invention is unlikely to increase viscosity during storage.

h: Maximum crest height

h _1/10 : 1/10 of the height of the maximum crest

t _h : hold time in the maximum crest height (h)

t _f : the holding time in 1/10 (h _1/10 ) of the maximum crest height (but, t _f <t _b )

t _b : the holding time in 1/10 (h _1/10 ) of the maximum crest height (but, t _f <t _b )

w _f : difference between t _h and t _f (t _h -t _f )

w _b : the difference _{between t b} and t _{h (t b} -t _h )

Fig. 1 is a chromatogram pattern that can be obtained by gel permeation chromatography measurement of polyalkylene glycol mono(meth)acrylate _{to illustrate w f} and w _b.

In this manual, "to" is used and the specified numerical range includes the values at both ends (upper limit and lower limit) of "to". For example, "2 to 4" means 2 or more and 4 or less.

In this specification, "(meth)acrylate" means acrylate or methacrylate. Here, only one type of (meth)acrylate may be used, or two or more types may be used together. Terms such as "(meth)acryloyl" also have the same meaning as "(meth)acrylate".

<PAG Mono(meth)acrylate>

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

CH ₂ =CR-COO-(AO) _n -H (1)

(In formula (1), R represents a hydrogen atom or a methyl group, and AO represents at least one of the oxyalkylene groups having 2 to 4 carbon atoms. When there are more than two types of AO, the additional form of _{(AO) n can be} Either segment or random, and n represents the average number of additional moles of oxyalkylene groups, ranging from 5 to 100).

AO is at least one of oxyalkylene groups having 2 to 4 carbon atoms. That is, AO is at least one selected from the group consisting of oxyethylene, oxyethylene, and oxyethylene. AO is preferably one or two types of oxyalkylene groups with 2 or 3 carbon atoms, more preferably oxyalkylene groups. n is the average number of additional moles of oxyalkylene groups. Therefore, n can have decimals. n is preferably from 5 to 60, more preferably from 5 to 50, more preferably from 5 to 40, and particularly preferably from 15 to 40.

<PAG mono(meth)acrylate gel permeation chromatography analysis characteristics>

The PAG mono(meth)acrylate of the present invention is characterized by: a chromatogram obtained by a gel permeation chromatography (GPC) measurement using a differential refractometer (vertical axis: refractive index intensity, horizontal axis ：Holding time) The calculated _{ratio of w b} to w _f , w _b /w _f, satisfies the relationship of the following formula (2):

0.25≦w _b /w _f ≦0.90 (2)

(In formula (2), among the peaks of the aforementioned chromatogram, the retention time in the maximum peak height (h) is set to be t _h and 1/10 of the maximum peak height (h _1/10 ). When set to t _f and t _b (but, t _f <t _b ), w _f represents the difference between t _{h and t f (t h} -t _f ), and w _b represents the difference between t _{b and t h (t b} -t _h ).)

For example, when w _b /w _{f is} less than 0.25, the molecular weight distribution of PAG mono(meth)acrylate may be largely biased toward the high molecular weight side, and the concentration of polymerizable functional groups may become low. The coincidence is reduced. From the viewpoint of polymerizability, w _b /w _f is preferably 0.30 or more, and more preferably 0.35 or more.

On the other hand, when w _b /w _{f is} greater than 0.90, the PAG mono(meth)acrylate of the present invention and the reaction solution containing the PAG mono(meth)acrylate of the present invention are easily gelled. 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 that changes by applying an external force to an object returns to its original state after the external force is removed. From the viewpoint of inhibiting gelation and strain resistance, the w _b /w _f system is preferably 0.80 or less, and more preferably 0.60 or less.

In the present invention, the _{tomogram used to calculate w b} /w _f (vertical axis: refractive index intensity, horizontal axis: retention time) uses HLC-8320GPC (registered trademark) as a gel permeation chromatograph (GPC) System, three continuous installations of SHODEX KF-G as protection column and SHODEX KF804L as separation column, separation column temperature 40℃, tetrahydrofuran as developing solvent, flow at a flow rate of 1 mL per minute, and inject PAG mono (methyl) 0.1 mL of 0.1% by weight tetrahydrofuran solution of acrylate, obtained by EcoSEC GPC calculation program.

<Production of PAG Mono(meth)acrylate>

The PAG mono(meth)acrylate of the present invention can be combined with ethylene oxide, propylene oxide, and epoxy in the presence of a complex metal cyanide complex catalyst (hereinafter also referred to as "DMC catalyst"). Butane (preferably propylene oxide) is added to the starting material (for example, 2-hydroxypropyl methacrylate) to produce. Specifically, the starting materials and DMC catalyst are added to the reaction vessel, and under the stirring of an inert gas environment, ethylene oxide, propylene oxide, and butylene oxide are added continuously or intermittently (hereinafter, this Etc. are collectively referred to as "alkylene oxides with 2 to 4 carbons") for addition polymerization. The alkylene oxide having a carbon number of 2 to 4 may be added under pressure, or it may be added under atmospheric pressure.

The average supply rate of alkylene oxides with 2 to 4 carbons is not limited, but it is desirable to change it according to the feed amount of alkylene oxides with 2 to 4 carbons. Specifically, the speed between the supply (supply amount per unit time) where the total supply of alkylene oxide with carbon numbers 2 to 4 is 5% to 20% by weight is set to V ₁ and carbon numbers 2 to 4 The total supply of alkylene oxide in excess of 20% by weight and the speed between the supply of 50% by weight or less is set to V ₂ , and the total supply of alkylene oxide with carbon numbers from 2 to 4 is in excess of 50% by weight and at 100 When the speed of the supply room below the weight% is set to V ₃ , in one aspect of the PAG mono(meth)acrylate used in the present invention, the average supply of alkylene oxides with carbon numbers 2 to 4 is used The speed control _{is preferably such that V 1} /V ₂ =1.1 to 2.0, and V ₂ /V ₃ =1.1 to 1.5. In addition, in another aspect of the production of the PAG mono(meth)acrylate of the present invention, the average supply rate of alkylene oxide having a carbon number of 2 to 4 is controlled so that V ₁ /V ₂ =0.4 to 0.9 , V ₂ /V ₃ =0.5 to 0.95 is better.

In addition, the reaction temperature for adding an alkylene oxide having a carbon number of 2 to 4 to the starting material is preferably 50 to 120°C, and more preferably 70°C to 90°C. When the reaction temperature is lower than 50°C, the reaction rate will become very small. If it is higher than 120°C, the polymerizable group in the starting material will be polymerized or colored.

Although there is no particular limitation on the amount of trace moisture contained in the starting materials and alkylene oxides with carbon numbers from 2 to 4, it is desirable that the amount of moisture contained in the starting materials is 0.5% by weight or less, which is contained in carbon number 2 The moisture content in the alkylene oxide up to 4 is 0.01% by weight or less.

Although the amount of DMC catalyst used is not particularly limited, it is preferably 0.000 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, relative to 100 parts by weight of the alkylene oxide derivative to be produced. The input of DMC catalyst in the reaction system can be carried out at the beginning, or it can be carried out in stages. After the polymerization reaction is over, the DMC catalyst is removed. The removal of the catalyst can be carried out by conventional methods such as filtration separation, centrifugal separation, and treatment with synthetic adsorbents.

In the production of PAG mono(meth)acrylate, DMC catalysts can be used conventionally. The DMC catalyst can use, for example, the one represented by the following formula (3):

M _a [M' _x (CN) _y ] _b (H ₂ O) _c ‧(L) _d (3)

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

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 them, it is better to use Zn(II).

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 them, Fe(II), Fe(III), Co(II), and Co(III) are preferably used.

The organic ligand L can be used: for example, alcohols, ethers, ketones, esters, etc., preferably alcohols. The preferred organic ligands are water-soluble ones. Specific examples include tertiary butanol, n-butanol, isobutanol, N,N-dimethylacetamide, and glycol dimethyl ether (glyme, glycerin). Diethylene glycol dimethyl ether), diethylene glycol dimethyl ether (diglyme) and the like. A particularly good DMC catalyst is Zn(II) ₃ [Co(III)(CN) ₆ ] ₂ (H ₂ O) ₄ (tertiary butanol) ₂ coordinated with tertiary butanol.

Addition of alkylene oxides having 2 to 4 carbon atoms in the reaction of the starting materials may use other additives within a range that does not impair the characteristics of the present invention. For example, as a polymerization inhibitor, hydroquinone (HQ), hydroquinone monomethyl ether (MQ), 2,6-di-tertiary butyl hydroxytoluene (BHT), and di-tertiary butyl can be added to the reaction system. Anisole (BHA), α-tocopherol, β-tocopherol, γ-tocopherol, etc. The polymerization inhibitor is preferably MQ and/or BHT, more preferably BHT. The amount of the polymerization inhibitor added is preferably 0.001 to 0.3 parts by weight relative to 100 parts by weight of the total of the starting material (for example, 2-hydroxypropyl methacrylate) and the alkylene oxide having 2 to 4 carbon atoms. When the addition amount is less than 0.001 parts by weight, the function of the polymerization inhibitor will be insufficient, and there is a possibility of gelation during the process of adding an alkylene oxide with a carbon number of 2 to 4. On the other hand, when the addition amount is more than 0.3 parts by weight, the purity of the obtained PAG mono(meth)acrylate may decrease.

<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 and other polymerizable compounds. Examples of other polymerizable compounds include (meth)acrylates that do not have PAG chains such as methyl acrylate and methyl methacrylate, acrylonitrile, methacrylonitrile, styrene, butadiene, and the like. Although the amount of PAG mono(meth)acrylate used during polymerization may vary depending on the application, it is preferably 10% by weight or more relative to the total of PAG mono(meth)acrylate and other polymerizable compounds. It is 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.

In order to obtain the polymerization form of the polymer of the present invention, solution polymerization, emulsion polymerization, bulk polymerization, etc. can be appropriately selected. The polymerization can be performed by conventional methods (for example, 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 type of polymerization initiator may be used, or two or more types may be used in combination.

Examples of thermal polymerization initiators include: tertiary butyl peroxytrimethylacetate, tertiary hexyl 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 (tertiary butyl peroxy) valerate, tertiary butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, di- Tertiary butyl peroxide, tertiary cumene peroxide, dicumyl peroxide, α,α'-bis(tertiary butylperoxy-m-isopropyl)benzene, Organic peroxides such as 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, benzyl peroxide, tert-butylperoxyisopropyl carbonate, etc. Or, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methyl Butyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) , 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(aminomethylazo)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-(2-propenyl)propionamidine ] Dihydrochloride, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-hydroxyethyl)-2-methyl Propanamidine] 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-diacrine Diazepine-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]propanamide}, 2,2'-Azobis{2 -Methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionyl Amine), 2,2'-azobis(2-methylpropanamide) dihydrate, 2,2'-azobis(2,4,4-trimethylpentane), 2,2' -Azobis(2-methylpropane), dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 2,2' -Azo compounds such as azobis[2-(hydroxymethyl)propionitrile].

The thermal polymerization using a thermal polymerization initiator can be performed in a temperature range and polymerization time that are usually performed. The amount of thermal polymerization initiator used is usually 0.0001 mol or more and 0.1 mol or less with respect to 1 mol of the polymerizable functional group ((meth)acryloyl group), preferably 0.001 mol or more and 0.1 mol or less. It is more preferably not less than 0.005 mol and not more than 0.1 mol.

Examples of the photopolymerization initiator include: 1-hydroxycyclohexane-1-yl phenyl 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-(methylsulfanyl)phenyl]-1-N-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -Alkylphenone compounds such as morpholinophenyl) butanone, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, bis(2,6-dimethoxybenzyl) Phosphonium)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide and other phosphine oxide compounds, 1,3- Aromatic peroxy ester compounds such as di(tertiary butyldioxycarbonyl)benzene and 3,3',4,4'-tetra(tertiary butyldioxycarbonyl)diphenyl ketone.

Photopolymerization can be carried out in the wavelength range of light and the irradiation time that is usually carried out. The amount of the photopolymerization initiator used is usually 0.0001 mol or more and 0.1 mol or less, and preferably 0.001 mol or more and 0.1 mol or less, relative to 1 mol of the polymerizable functional group (methyl(acryloyl) group). , More preferably 0.005 mol or more and 0.1 mol or less. In photopolymerization, sensitization using pigments can be performed.

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 million, more preferably 4,000 to 4 million, and even more preferably 5,000 to 3 million. The aforementioned weight average molecular weight is a value measured with a gel permeation chromatograph under the above-mentioned conditions.

<Composition for Film>

The present invention provides a film composition, which contains the following components (A) and (B), wherein:

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

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

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

(Component (B)) Multifunctional (meth)acrylate monomer.

<Ingredient (A)>

The 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 be used alone or in combination of two or more kinds.

From the viewpoint of suppressing thickening, the content of component (A) is 20 to 50% by weight, preferably 25 to 50% by weight, and more preferably 30 to 50% by weight, relative to the total of component (A) and component (B). good. In addition, from the viewpoint of suppressing thickening, the content of the component (A) relative to the entire composition is preferably 10 to 50% by weight, and more preferably 20 to 50% by weight.

<Ingredient (B)>

The component (B) of the film composition of the present invention is a polyfunctional (meth)acrylate monomer and is a component that improves the curability of the film composition. Here, "multifunctional (meth)acrylate" refers to a (meth)acrylate having two or more (meth)acryloyl groups in one molecule. In addition, the "bifunctional (meth)acrylate" described later refers to a (meth)acrylate having two (meth)acrylic groups in one molecule. "Trifunctional (meth)acrylate" and the like also have the same meaning as "bifunctional (meth)acrylate".

As for the component (B), only 1 type may be used, and 2 or more types may be used together. Component (B) includes, for example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, 1,6-hexanediol di(methyl) ) Alkyl glycol di(meth)acrylates such as acrylate, 1,9-nonanediol di(meth)acrylate; polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylic acid Ester, polybutylene glycol di(meth)acrylate and other polyalkylene glycol di(meth)acrylic acid Esters; neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol 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, polyurethane di(meth)acrylate and other alkanediol di(meth) Bifunctional (meth)acrylates other than acrylate and polyalkylene glycol di(meth)acrylate; trimethylolpropane tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate Yl)acrylate, ε-caprolactone modified tris((meth)acryloyloxyethyl)isocyanurate and other trifunctional (meth)acrylates; di-trimethylolpropane tetra( 4-functional (meth)acrylates such as meth)acrylate; 5-functional (meth)acrylates such as dineopentaerythritol penta(meth)acrylate; Dineopentaerythritol hexa(meth)acrylate, etc. 6-functional (meth)acrylate and the like. Among these, alkanediol di(meth)acrylate is preferred, and butanediol di(meth)acrylate is more preferred.

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

<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 kinds. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator. Both of the thermal polymerization initiator and the photopolymerization initiator may be used only one type, or two or more types may be used in combination. Examples of the thermal polymerization initiator and the photopolymerization initiator include those described above.

With respect to 1 mol of the polymerizable functional group ((meth)acryloyl group) in the film composition of the present invention, the content of the polymerization initiator is preferably 0.0001 mol or more and 0.1 mol or less, and 0.001 mol It is more preferably 0.1 mol or more, and more preferably 0.005 mol or more and 0.1 mol or less.

<Monofunctional (meth)acrylate monomer>

From the viewpoint of suppressing thickening, the film composition of the present invention preferably contains a monofunctional (meth)acrylate monomer other than polyalkylene glycol mono(meth)acrylate.

Monofunctional (meth)acrylate monomers may be used alone or in combination of two or more. Examples of monofunctional (meth)acrylate monomers include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate Base) n-butyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, (meth) ) Stearyl acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate Ester, tert-butylcyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, etc. Among these, methyl (meth)acrylate is preferred.

When a monofunctional (meth)acrylate monomer is used, its content 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 20 to 40 parts by weight. Better.

<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 a 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, phenol resins, Phenolic phenolic resin, cresol phenolic resin, etc., antistatic agent, antioxidant, rubber, silica particles, zirconia, plasticizer, ultraviolet absorber, defoamer, thixotropic agent, release agent, filler Agents, phosphors, pigments, etc. Other ingredients can be used only one type, or more than two types can be combined use.

Relative to the entire composition, the content of other components is preferably 20% by weight or less, more preferably 15% by weight or less, and more preferably 10% by weight or less. Here, "the content of other components is 20% by weight or less with respect to the entire 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 with respect to the entire composition. Other similar expressions also have the same meaning.

<Use of film>

The uses of the film obtained from the film composition of the present invention include, for example, 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, photoelectric crystals, solar cells, dry film resists, projectors, home appliances, automobiles, locomotives, heavy machinery, railway vehicles, ships, building materials, smoke-proof hanging walls, smoke-proof curtains , Decorative panels and other components.

[Example]

Hereinafter, examples and the like are listed to explain the present invention in detail.

Synthesis Example 1: Synthesis of composite metal cyanide complex (DMC) catalyst

15 mL of an aqueous solution containing 0.84 g of potassium hexacyanocobaltate K ₃ Co(CN) ₆ was stirred at 40° C., and dropped into 2.0 mL of an aqueous solution containing 2.1 g of zinc chloride over 15 minutes. After the dropping, 16 mL of water and 16 g of tert-butanol 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 (the first time) was performed to obtain a solid. 14 mL of water and 8.0 g of tert-butanol were added to this solid, and after stirring for 30 minutes, a filtration operation (second time) was performed to obtain a solid.

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

Example 1: Synthesis of Compound 1

A stainless steel 5-liter (4,890 mL) pressure-resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen blowing pipe, agitator, vacuum exhaust pipe, cooling coil, and steam jacket is fed with methyl 500 g of 2-hydroxypropyl acrylate (moisture content 0.02% by weight), 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). After replacing with nitrogen, the temperature was raised to 70°C, and while stirring under 0.3 MPa or less, 403 g of propylene oxide (methyl ethylene oxide, moisture content 0.005 wt%) was dropped from the nitrogen blowing pipe, and the inside of the reaction tank was observed After changing the pressure and temperature with time, the pressure in the reaction tank was drastically reduced 5 hours after the completion of the dripping of 403g of propylene oxide. Then, while maintaining the inside of the reaction tank at 70° C., under the condition of 0.5 MPa or less, 1,132 g of propylene oxide was slowly dropped from the nitrogen blowing pipe. In addition, the average supply rate is 260 g/hour for _{V 1} , 203 g/hour for _{V 2} , and 152 g/hour for _{V 3 (V 1} /V ₂ =1.28, V ₂ /V ₃ =1.34). After the dropping was completed, the reaction was carried out at 70° C. for 0.5 hours, and then the reaction mixture was taken out from the reaction layer, and the reaction mixture was filtered to remove solids, and liquid compound 1 was obtained. The obtained compound 1 was subjected to gel permeation chromatography measurement using the above-mentioned HLC-8320GPC (registered trademark).

Examples 2 to 4: Synthesis of Compounds 2 to 4

Compounds 2 to 4 were synthesized in the same manner as the synthesis of compound 1, except for the additional moles of propylene oxide, or the additional moles of propylene oxide and the starting materials. In the same manner as above, the obtained compounds 2 to 4 were subjected to gel permeation chromatography measurement.

Examples 5 to 8: Synthesis of compounds 5 to 7

In addition to using ethylene oxide and propylene oxide, or 1,2-butylene oxide instead of propylene oxide as alkylene oxide, changing the number of additional moles of alkylene oxide, and using those described in Table 1 below as the starting point Compounds 5 to 7 were synthesized in the same way as the synthesis of compound 1 except for the starting materials. In the same manner as above, the obtained compounds 5 to 7 were subjected to gel permeation chromatography measurement. Furthermore, in Example 5, propylene oxide was added to the starting material first, and then a mixture of ethylene oxide and propylene oxide was added, and _{the addition form of (AO) n} was synthesized as random compound 5. In addition, in Example 6, first, propylene oxide was added to the starting material, and then ethylene oxide was added to synthesize compound 6 in which the added form of _{(AO) n was a block.}

Comparative Example 1: Synthesis of Compound 8

A stainless steel 5-liter (4,890 mL) pressure-resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen blowing pipe, agitator, vacuum exhaust pipe, cooling coil, and steam jacket is fed with methyl 500 g of 2-hydroxypropyl acrylate, 17.6 g of boron trifluoride diethyl ether complex, and 0.6 g of hydroquinone monomethyl ether (MQ). After replacing with nitrogen, the temperature was raised to 60°C, and while stirring under the condition of 0.3 MPa or less, 1,578 g of propylene oxide (methyl ethylene oxide) was dropped from the nitrogen blowing pipe. After the dripping was completed, it was allowed to react at 60°C for 0.5 hours, and after adding water and hexane, it was neutralized with an aqueous sodium hydroxide solution. After the water layer was removed, hexane and water were distilled off under reduced pressure, and the concentrate was filtered to remove solids to obtain compound 8 in a liquid state. The same operation as above was carried out, and the obtained compound 8 was subjected to the gel permeation chromatography measurement.

Comparative Examples 2 and 3: Synthesis of Compounds 9 and 10

Compounds 9 and 10 were synthesized in the same manner as the synthesis of compound 8 except for the additional moles of propylene oxide or the additional moles of propylene oxide and the starting materials. The same operation as above was performed, and the obtained compounds 9 and 10 were subjected to the gel permeation chromatography measurement.

The starting materials used in the synthesis of compounds 1 to 10, w _b /w _f obtained from the chromatograms obtained from compounds 1 to 10, and the characteristics 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.

[Table 1]

(Assessment 1 to inhibit gelation)

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 aforementioned compound was weighed in a spiral tube, and the spiral tube containing the aforementioned compound was placed in a constant temperature bath at 150°C under a nitrogen atmosphere. Time (gelation time). After the spiral tube is put into the thermostat, check the state of the compound in the spiral tube every 10 minutes (maximum: 180 minutes). When the spiral tube is horizontal, the time when the aforementioned compound does not flow and gels is judged visually as the "gelation time" ", the gelation inhibition was evaluated according to the following criteria. The results are shown in Table 2. In addition, since Compound 1 did not gel even if it was put into the thermostatic bath from the spiral tube for 180 minutes, the gelation time was set to "180 minutes or more".

<Evaluation criteria for gelation inhibition>

◎: Gelation time is 120 minutes or more

○: Gelation time is 60 minutes or more and 110 minutes or less

×: Gelation time is less than 50 minutes

[Table 2]

(Assessment of gelation inhibition 2)

The gelation inhibition of the reaction solution containing the compounds 1 to 7 obtained in Examples 1 to 7 and the 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, polypropylene glycol dimethacrylate (the average additional mole of oxypropylene Number: 7) 0.15 g, 3 mL of solvent (toluene), and polymerization initiator ("V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) relative to 1 mol of polymerizable functional group (meth (acryloyl) group) , 2,2'-Azobis(2,4-dimethylvaleronitrile)) 0.01 mol was put into a test tube (10mL) with a cap to prepare the reaction solution, the resulting reaction solution was bubbled with nitrogen, and the cap Seal the test tube. 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 rate of 100 times per minute. After the test tube is put into the thermostat, check the state of the reaction solution in the test tube every 10 minutes (maximum: 180 minutes). When the test tube is horizontal, the time when the reaction solution does not flow and gels is judged visually as "gelation" Time", the gelation inhibition was evaluated based on the following criteria. The results are shown in Table 3. In addition, the reaction solution that did not gel after being poured into the thermostat for 180 minutes from the test tube, the gelation time was set to "180 minutes or more".

<Evaluation criteria for gelation inhibition>

◎: Gelation time is 120 minutes or more

○: Gelation time is 60 minutes or more and 110 minutes or less

×: Gelation time is less than 50 minutes

[table 3]

Example 8: Synthesis of polymer 1

10g of the compound 1 obtained in Example 1 and a polymerization initiator ("V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 2 ,2'-even Nitrobis(2,4-dimethylvaleronitrile)) 0.01 mol was put into a petri dish, stirred with a glass rod to prepare a mixture, and the resulting mixture was heated at 70°C under a nitrogen atmosphere for 3 hours to synthesize a polymer 1. The weight average molecular weight of the obtained polymer 1 was measured by the above-mentioned gel permeation chromatograph.

Examples 9 to 14 and Comparative Examples 4 to 6: Synthesis of polymers 2 to 10

Except that any one of compounds 2 to 10 was used in place of compound 1, polymers 2 to 10 were synthesized in the same method as the synthesis of polymer 1.

(Evaluation of strain resistance)

The strain resistance of the polymers 1 to 10 obtained in Examples 8 to 14 and Comparative Examples 4 to 6 was evaluated with a viscoelasticity measuring device MCR302 and a measuring probe (cone plate, PP25) (manufactured by Anton Pearl). Specifically, the storage modulus G'when the shear strain γ of the polymer changes from 0.01 to 100 at 20°C is measured. The shear strain γ when the storage modulus G'changes is taken as γ _max , and the strain resistance is evaluated according to the following evaluation criteria. Due to the shape or volume of the polymer by the application of an external force is changed, when an external force is removed returns to its original state to the γ _max, so the γ _max greater the resistance the better contingency.

<Evaluation criteria for strain resistance>

◎: γ _max is 40 or more

○: γ _max is 30 or more and less than 40

×: γ _{max is} less than 30

The evaluation results of the compounds used in the synthesis of polymers 1 to 10, and the weight average molecular weight, γ _max, and strain resistance of polymers 1 to 10 are shown in Table 4.

[Table 4]

Example 15 and Comparative Example 7: Manufacture of composition for thin film

The compounding amount shown in Table 5 below was used to prepare a film composition.

(Assessment of viscosity increase inhibition of composition)

The thin film compositions obtained in Example 15 and Comparative Example 7 were evaluated for their suppression of thickening. Specifically, the aforementioned composition was put into a constant temperature bath at 50°C in an atmospheric environment and heated for 2 hours. Measure the viscosity of the composition before heating (hereinafter referred to as "viscosity before heating") and after heating using a RE-85 viscometer (Toki Sangyo Co., Ltd.) at a temperature of 25°C and a rotor speed of 10 rpm. The viscosity of the composition (hereinafter referred to as "Viscosity after heating") is given by the following formula:

Viscosity change rate = viscosity after heating / viscosity before heating

Determine the rate of change in viscosity. In addition, the viscosity increase suppression of the composition was evaluated based on the following criteria. The results are shown in Table 5.

<Assessment criteria for viscosity increase inhibition of composition>

○: Viscosity change rate does not reach 1.10

×: The viscosity change rate is 1.10

[table 5]

[Industrial availability]

According to the present invention, a polyalkylene glycol mono(meth)acrylate can be provided, which can inhibit gelation during polymer production. The polymer obtained from the polyalkylene glycol mono(meth)acrylate of the present invention 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 multifunctional (meth)acrylate monomers of the present invention is not easy to increase the viscosity during storage, so the film obtained therefrom can be used for Various uses.

This application is based on Japanese Patent Application No. 2020-19618 filed in Japan, and its content is completely included in the specification of this application.

Claims (4)

A polyalkylene glycol mono(meth)acrylate, represented by the following formula (1), and the ratio _{of w b} to w _{f calculated from the chromatogram obtained by the gel permeation chromatography measurement w b} /w _f system satisfies the relationship of the following formula (2), CH ₂ =CR-COO-(AO) _n -H In formula (1), R represents a hydrogen atom or a methyl group, and AO represents at least one of the oxyalkylene groups having 2 to 4 carbon atoms. When there are more than two types of AO, the additional form of _{(AO) n can be embedded} Any one of segment or random, and n represents the average number of additional moles of oxyalkylene groups, ranging from 5 to 100, 0.25≦w _b /w _f ≦0.90 (2) In formula (2), among the peaks of the aforementioned chromatogram, the holding time in the maximum peak height (h) is set to t _h and two of the holding time in 1/10 (h _{1/10) of the maximum peak height are set.} and when t _f to t _b, w _f and _h represents the difference t of t _f (t _h -t _f), and w _b t _B and t represents the difference of _h (t _b -t _h), but t _f <t _b . The polyalkylene glycol mono(meth)acrylate according to claim 1, wherein AO in the formula (1) is one or two types of oxyalkylene groups having 2 or 3 carbon atoms. A polymer obtained by polymerizing the polyalkylene glycol mono(meth)acrylate described in claim 1 or 2. A composition for thin films, a composition for thin films containing the following components (A) and (B), wherein: The content of component (A) is 20 to 50% by weight relative to the total of component (A) and component (B), and The content of component (B) is 50 to 80% by weight relative to the total of component (A) and component (B): Component (A): the polyalkylene glycol mono(meth)acrylate as described in claim 1 or 2, and Component (B): Multifunctional (meth)acrylate monomer.

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