JPS61195110A - Urethane (meth)acrylate polymer, its production and composition containing same - Google Patents

Abstract

PURPOSE:The reaction of a specific (meth)acrylate oligomer bearing hydroxyl with an organic compound bearing isocyanate groups gives the titled prepolymer which is used as coating, adhesive, ink, hard coat or resist. CONSTITUTION:(A) A (meth)acrylate oligomer of formula I (R<1> is H, methyl; Z is divalent organic group of 2-20 carbon atoms; p is 1-100) is allowed to react with (B) an organic compound bearing isocyanate groups of formula II [Y is residue of (1+m+n) valent organic compound bearing isocyanate groups; l+m+n is 1-6] and, when needed, (C) an organic compound bearing hydroxyl groups other than those of formula I, to give the objective prepolymer of formula III [R<2> is organic group bearing hydroxyl where oligomers of formula I is excluded; l is 1-6, n is 0-5].

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel urethane (meth)acrylate prepolymer, a method for producing the same, and a composition containing the same.
More specifically, a novel urethane (meth)acrylate prepolymer that has excellent viscosity characteristics and cured physical properties and is useful for various uses, and a method for producing the prepolymer using a specific hydroxyl group-containing (meth)acrylate oligomer as a raw material. The present invention relates to a composition containing the prepolymer.

[Conventional technology]

Urethane (meth)acrylate prepolymer, so-called urethane (meth)acrylate, is an important component in the production of thermosetting resins or photocuring resins, and is used in a wide range of applications such as paints, adhesives, inks, hard coats, and resists. Urethane (meth)acrylate prepolymers are generally produced by reacting polyols, polyisocyanates, and hydroxyalkyl (meth)acrylates. A vast variety of urethane (meth)acrylate prepolymers have been synthesized by changing the It was necessary to add a reactive diluent to these prepolymers.Furthermore, none of these prepolymers had excellent cure speed, hardness, adhesion, and other properties of the cured product. There is a need for the development of urethane (meth)acrylate prepolymers that have low viscosity, high curing speed, and excellent cured physical properties such as hardness and adhesion of the cured product.

[Problem that the invention seeks to solve]

The present inventors conducted various studies in view of the above circumstances, and as a result, arrived at the present invention. Accordingly, the present invention relates to a novel urethane (meth)acrylate prepolymer having a specific structure that can be used in various applications, a method for producing the same, and a composition containing the same.

[However, in the formula, R1#'' is a hydrogen atom or a methyl group, and may be the same or stationery, and Z is a divalent organic group having 2 to 20 carbon atoms, and each is the same. may also be used as stationery, p is an integer from 1 to 100, and R2Fi is a residue of a hydroxyl group-containing organic compound (excluding a hydroxyl group-containing (meth)acrylate oligomer represented by the following general formula (II)). Yes, l is an integer from 1 to 6, m is 0 or an integer from 1 to 5, n is an integer from 0 or 1 to 5, and !0m+ru is an integer from 1 to 6. Ashi and Y are (1+m+a)-valent incyanate group-containing organic compound residues.]

A urethane (meth)acrylate prepolymer represented by

(Note) (In the formula, R1 is a hydrogen atom or a methyl group,
They may be the same or serve as stationery; 2 is a divalent organic group having 2 to 2 carbon atoms; they may be the same or serve as stationery; P is an integer from 1 to 100; be. ) Hydroxyl group-containing (meth)acrylate oligomer (2) General formula (n) CHrC-C-0-Z-0-(CH, -CH-C-0-
Z-0)-H(n) (In the formula, R1 is a hydrogen atom or a methyl group, which may be the same or stationery, and 2 is a divalent organic compound having 2 to 2 carbon atoms. The bases may be the same or stationery, and P is 1.
It is an integer between ~100. ) Hydroxyl group-containing (meth)acrylate oligomers represented by the general formula Y-+
NC0)l+m+.

(However, in the formula, Y is a (/ + m + n )-valent incyanate group-containing organic compound residue, and 73-)-m
+ru is an integer from 1 to 6. ) and, if necessary, the above general formula (
General formula (1) characterized by reacting a hydroxyl group-containing organic compound (C) other than the hydroxyl group-containing (meth)acrylate oligomer (4) represented by II) [wherein R1 is a hydrogen atom or methyl 2 is a divalent organic group having 2 to 20 carbon atoms and may be the same or stationery, and p is 1 to Zoo. is an integer, and R2 is a hydroxyl group-containing organic compound (however, a hydroxyl group-containing (meth) compound represented by the general formula (II) above)
Excludes acrylate oligomers. ), l is an integer of 1 to 6, wind is 0 or an integer of 1 to 5, ru is 0 or an integer of 1 to 5, l + m + ru is an integer of 1 to 5.
A method for producing a mer containing an isocyanate group, where Y is an integer of 6 and Y is <i+m+rL).

(3) General formula (1) [In the formula, R1 is a hydrogen atom or a methyl group, and may be the same or stationery, and z is a divalent organic group having 2 to 20 carbon atoms. Hydroxyl group-containing (
Expansion and removal of meth)acrylate oligomers. ), l is an integer of 1 to 6, mJdQ or an integer of 1 to 5, l is 0 or an integer of 1 to 5, l+m+
is an integer of 1 to 6, and Y is a residue of an incyanate group-containing organic compound having a valence of (l+m+rL). ] A composition whose main components are a urethane (meth)acrylate prepolymer represented by the following and an ethylenically unsaturated compound.

This is related to K.

More briefly, the present invention relates to a urethane (meth)acrylate prepolymer obtained by reacting an incyanate group-containing compound with a compound containing a hydroxyl group and an unsaturated group, which contains a hydroxyl group and an unsaturated group. A novel urethane (meth)acrylate prepolymer characterized by using a specific hydroxyl group-containing (meth)acrylate oligomer (4) represented by the above general formula (II) as a compound, a method for producing the same, and the same. The present invention relates to a composition containing the following.

The hydroxyl group-containing (meth)acrylate oligomer represented by the general formula (II) used in the present invention is represented by the general formula (II) (wherein, R1 is a hydrogen atom or a methyl group, and 2 is a carbon atom having 2 to 20 carbon atoms. It is obtained from K when a hydroxyl group-containing (meth)acrylate represented by (a) is an organic group with a valence of 1. Specific examples of the hydroxyl group-containing (meth)acrylate represented by general formula (1) include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, acrylate, diethylene glycol monomethacrylate , dipropylene glycol monoacrylate, diethylene glycol monomethacrylate,
Examples include hydroxycyclohexyl acrylate and hydroxycyclohexyl methacrylate. These may be used alone or as a mixture. K, which is oligomerized by addition polymerization of hydroxyl group-containing (meth)acrylate, is disclosed in, for example, Japanese Patent Application No. 59-256558.
A hydroxyl group-containing (meth)acrylate as described in No. 1, a protonic acid such as sulfuric acid or para-toluenesulfonic acid;
Lewis acid such as boron trifluoride, tin tetrachloride, etc. Oxysulfate such as titanium dioxysulfate: 10 to 150 It is sufficient to maintain the temperature at ℃.

Other than the hydroxyl group-containing (meth)acrylate oligomer represented by the general formula (n), the incyanate group-containing organic compound (B) represented by the above general formula, and if necessary the hydroxyl group-containing (meth)acrylate oligomer (4) By reacting the hydroxyl group-containing organic compound (C), the urethane (meth)acrylate prepolymer of the present invention can be obtained.

The incyanate group-containing organic compounds used in the present invention include monoisocyanates (Bl) listed below.
, polyisocyanates (B2), and prepolymers containing terminal incyanate groups (B3), and these compounds can be used alone or as a mixture. Furthermore, among these organic compounds containing incyanate groups (B), compounds containing two or more incyanate groups in the molecule are collectively referred to as polyisocyanate group-containing organic compounds (B4).

Examples of monoisocyanates (Bl) include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, chloroethyl isocyanate, isocyanatoethyl methacrylate, octadecyl isocyanate, phenyl isocyanate, ethoxyphenyl isocyanate, chlorophenyl isocyanate, benzyl isocyanate, Examples of polyisocyanates (B2) such as naphthyl isocyanate and dichlorophenyl isocyanate include ethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, phthadecamethylene diisocyanate, ')y'>''!isocyanate, o-1nt- or P-phenylene diisocyanate, 4-ingrovir-1゜3-7 2-2 diisocyanate, 4-methoxy 1,3-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, m
- or P-tetramethelxylylene diisocyanate, 1.5-naphthylene diisocyanate, 4.4'-
diphenylmethane diisocyanate), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate), 2
．． 4-Diincyanate diphenyl ether, 3.3'
-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, triphenylmethane triisocyanate,
Tris-(p-isocyanatophenyl) thiophosphite, polymethylene polyphenyl isocyanate (novolac type polyisocyanate), 1,4-cyclohexylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated 4 .4'
-diphenylmethane diisocyanate), 1,5-tetrahydronaphthalene diisocyanate, inphorone diisocyanate, diphenylsulfone diisocyanate, 1
, 6-hexamethylene diisocyanate dimer and 2.4
- Incyanate polymers such as tolylene diisocyanate dimer, crude products of tolylene diisocyanate and 4゜4'-diphenylmethane diisocyanate, and other terminal isocyanate group-containing prepolymers (B3) include:
The above polyincyanates (B2), the polyols (C1) listed below, and the polyether polyols (C
2), polyester polyols (C3), ester diols (C4), polyolefin polyols (C5
) and a hydroxyl group-containing compound such as polycarbonate polyols (C6) at a ratio of isocyanate group number/hydroxyl group number greater than 1.0. Can be done.

Examples of the polyols (C1) used in the synthesis of the terminal incyanate group-containing prepolymers (B3) include ethylene glycol, propylene glycol, trimethylene glycol, 1.2-11.3- or 1.4- Butanediol, 1,5-bentanediol, hexanediol, neopentyl glycol, dibromneopentyl glycol, trimethylbentanediol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, cyclohexanediol, cyclohexane dimetatool, Glycerin, diglycerin, sorbitol, trishydroxyethyl in cyanurate, bisphenol A, 2,2'-di(4
-Hydroxypropoxyphenyl)propane, hydrogenated bisphenol A1)liethanolamine, N.

Polyether polyols (C2) such as N, N′-tetrakis(β-hydroxyethyl)ethylenediamine, etc.
Examples of polyester polyols (C3) include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, diethylene glycol, etc. Examples of polyester polyols (C3) include the above polyols (
C1) and/or polyether polyols (C2
) and polycarboxylic acids (e.g. phthalic anhydride, maleic anhydride, succinic anhydride, dodecynylsuccinic anhydride, citraconic anhydride, trimellitic anhydride, pyromellitic anhydride, methylcyclohexenetricarboxylic anhydride, tetrahydrophthalic anhydride) , hexahydrophthalic anhydride, hymic anhydride, tetrachlorophthalic anhydride, hetonic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, maleic acid, hexamaric acid, succinic acid, adipic acid, azelaic acid, sepatenoic acid, trimellitic acid Examples include polyester polyols obtained by reacting hydroxyl groups/carboxyl groups with a hydroxyl group/carboxyl group ratio of more than 1.0, such as bis(2-hydroxyethyl) terephthalate.

-dimethyl-3-hydroxypropionate (hydroxybivalylhydroxybipare)), 2゜2-dimethyl-4-hydroxybutyl-2,2-dimethyl-4-hydroxybutyrate, 2-ethyl-2-methyl- Polyolefin polyols (such as 3-hydroxypropyl 2-ethyl-2-methyl-3-hydroxypropionate)
Examples of C5) include polybutadiene polyol, etc.
Examples of polycarbonate polyols (C6) include:
Examples include reaction products of 1,6-hexanediol and ethylene carbonate.

Furthermore, the polyols (C1), polyether polyols (C2), polyester polyols (C3), ester diols (C4), polyolefin polyols (C5) or polycarbonate polyols (C
6), cyclic compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, higher fatty acid monoepoxide, epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, glycidol, phenyl glycidyl ether, tetrahydro-7rane, ε-caprolactone, etc. alone or Hydroxyl group-containing compounds obtained by ring-opening addition reactions of mixtures, such as ethylene oxide addition products to trimethylolpropane, ε-caprolactone addition products to neopentyl glycol, terminals produced from butylene glycol, azelaic acid, and isophthalic acid. Butyl glycidyl ether addition reaction product to hydroxyl group-containing polyester polyol, ε-caprolactone addition reaction product to hydroxypivalyl hydroxybiparate, propylene oxide addition reaction product to polybutadiene diol, 1゜6-hexanediol and ethylene oxide- )(1:1) An ethylene oxide addition reaction product to the reaction product can also be reacted with polyisocyanates (B2) to form prepolymers containing terminal isocyanate groups (B3). The ring-opening addition reaction of a cyclic compound can be carried out by a known method, and it is generally desirable to carry out the reaction in the presence of a catalyst. As such a catalyst, a Lewis acid, an organic titanium compound, an organic tin compound, etc. can be used.

The hydroxyl group-containing organic compound (C) used if necessary in the present invention contains at least one hydroxyl group capable of reacting with an isocyanate group other than the above-mentioned hydroxyl group-containing (meth)acrylate τ oligomer (4). Any organic compound can be used without particular restrictions. Examples of the hydroxyl group-containing organic compound (C) include the above-mentioned polyols (C1), polyether polyols (C2), and polyester polyols (C1) used to obtain the terminal isocyanate group-containing prepolymers (B3).
C3), ester diols (C4), polyolefin polyols (C5), polycarbonate polyols (C6), and their cyclic compound addition reaction products (hereinafter, these are collectively referred to as polyol compounds (C1 to 6)); Aliphatic alcohols such as methanol, ethanol, propatool, and butanol; (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; ) alkylene glycol monoalkyl esters and the like. In addition, unsaturated acid partial esters of polyol compounds (C1-6) such as 1,
4-butanediol mono(meth)acrylate, 16-
Hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate , pentaerythritol tri(
meth)acrylate, glycerin mono(meth)acrylate, diglycerin tri(meth)acrylate, hydrogenated bisphenol A mono(meth)acrylate, di(meth)acrylate of trimethylolpropane added with 6 moles of ethylene oxide, hydroxyethyl(meth)acrylate, Hydroxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.; cyclic compounds to hydroxyalkyl(meth)acrylate (Aliphatic glycidyl ethers such as butyl glycidyl ether, allyl glycidyl ether, aromatic glycidyl ethers such as phenyl glycidyl ether, epichlorohydrin, ε-caprolactone, tetrahydrofuran, etc.) Adducts such as ε-caprolactone addition hydroxyalkyl (meth)acrylates in case ε-caprolactone 2
Molar addition hydroxyethyl (meth)acrylate, etc.; addition reaction product of a compound having an epoxy group and a compound having an ethylenically unsaturated group, such as butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, shrimp chlorohydrin 1 glycidyl (meth) ) Addition reaction products of monoepoxides such as acrylates and (meth)acrylic acid, ethylene glyfur diglycidyl ether, polyethylene glycol diglycidyl ether, Prohillenc IJ col diglycidyl ether, neopentyl glycol diglycidyl ether, N, N- Compounds containing a hydroxyl group and an ethylenically unsaturated group in the molecule, such as an addition reaction product of a polyepoxide such as diglycidylaniline and (meth)acrylic acid, can also be used as the hydroxyl group-containing organic compound (C). Of course. The hydroxyl group-containing organic compound (C) can be selected from those listed above alone! It can be used as a mixture.

A known manufacturing method can be used for manufacturing the urethane (meth)acrylate prepolymer of the present invention. That is, the reaction of the hydroxyl group-containing (meth)acrylate oligomer (4) represented by the general formula (U) with the isocyanate group-containing organic compound Φ), or the reaction of the hydroxyl group-containing (meth)acrylate oligomer represented by the general formula CI) It can be produced by the reaction between the hydroxyl group-containing organic compound (C) and the polyisocyanate group-containing organic compound (B4).

The ratio of these raw materials can be charged depending on the urethane (meth)acrylate prepolymer to be obtained, but
Usually, the ratio of the number of incyanate groups/the number of hydroxyl groups may be in the range of 1.0±0.1. but,
If the hydroxyl group-containing organic compound (C) is used in large excess, the hydroxyl group-containing organic compound residue will contain a hydroxyl group.

In addition, it is also free to use compounds having other functional groups such as hydroxyl groups in addition to the incyanate group (in the incyanate group-containing organic compound), and in that case,
The isocyanate group-containing organic compound residue represented by Y in general formula (1) may contain other functional groups.

There is no particular restriction on the order of addition of the raw materials, but the above polyol compound (C) as the hydroxyl group-containing organic compound C)
When using 1 to 6), it is convenient to react the polyol compound (C1 to 6) and the polyisocyanate group-containing organic compound (B4) in advance. An embodiment of the production method of the present invention includes, for example, (a) a method of reacting a hydroxyl group-containing (meth)acrylate oligomer (4) represented by general formula (n) with an incyanate group-containing organic compound (ii).

(b) After reacting the hydroxyl group-containing (meth)acrylate oligomer (4) represented by general formula (II) with the polyisocyanate group-containing organic compound (B4) in a proportion such that incyanate groups remain. , a hydroxyl group-containing anate group-containing organic compound (B4) in a proportion such that incyanate groups remain, and then a hydroxyl group-containing (meth)acrylate oligomer represented by the general formula (It) is prepared. A method of reacting (A).

(b) After reacting the hydroxyl-based isocyanate group-containing organic compound (B4) represented by the general formula (n) with the reactive anate group-containing organic compound (B4) in a proportion such that the isocyanate group remains, the general formula The human ``roxyl group-containing (meth)acrylate oligomer (4) represented by (It) is reacted in such a proportion that the incyanate group remains, and then the incyanate group-containing organic compound (B4) is reacted with the hydroxyl group-containing organic compound (B4). After reacting using such proportions that the groups remain, general formula (n)
a hydroxyl group-containing (meth)acrylate oligomer integrally represented by) and a hydroxyl group-containing organic compound (C)
A method of reacting a mixture with.

After reacting with a cyanate group-containing organic compound (B4) in a ratio such that isocyanate groups remain, reacting with a hydroxyl group-containing organic compound (C) in a ratio such that incyanate groups remain, A method of then reacting a hydroxyl group-containing (meth)acrylate oligomer (4) represented by general formula (II).

(g) Hydroxyl group-containing (
After reacting the meth)acrylate oligomer (4) with the R isocyanate group-containing organic compound (B4) in such a proportion that the incyanate group remains! A method in which a isocyanate group-containing organic compound (B4) is blended and then a hydroxyl group-containing organic compound (C) is reacted.

After reacting with the cyanate group-containing organic compound (B4) in a proportion such that the isocyanate group remains, the 51 socyaneto group-containing organic compound (B4) is blended, and then the hydroxyl group represented by the general formula (If) is added. Examples include a method of reacting a mixture of the containing (meth)acrylate oligomer (4) and the hydroxyl group-containing organic compound (C), but the present invention is not limited to these embodiments.

The reaction in the present invention is carried out at 10-tSO°C, especially at 30-10°C.
Preferably, the temperature is 0°C.

If the reaction temperature is high, the polymerization reaction of the vinyl groups in the raw materials and the reaction product tends to occur. If the reaction temperature is too low, the reaction rate will be low. Furthermore, in order to avoid polymerization of vinyl groups in the raw materials and reaction products, it is preferable to carry out the reaction in the presence of a polymerization inhibitor. Examples of polymerization inhibitors include nohydroquinone, hydroquinone monomethyl ether, F-benzoquinone, methylhydroquinone, t-butylhydroquinone, di-t-butylnohydroquinone, t-butylcatechol, phenothiazine, N, l'r-di2- Naphthyl-P-phenylenediamine, 4,6-sinitro O-cresol, N-nitrosodiphenylamine, α-
Examples include naphthol and copper salts. Its usage is usually
It is 0.005 to 1% by weight based on the raw material. Furthermore, in the reaction of the present invention, known catalysts such as organic tin compounds such as diptyltin dilaurate and dioctyltin dilaurate or tertiary amines are used to promote the urethanization reaction between incyanate groups and hydroxyl groups. can be carried out in the presence of Incidentally, the reaction may be carried out in a suitable solvent if necessary. The solvent is not particularly limited, but examples include styrene, vinyl acetate, methyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and Ethelene glycoldi (meth)
Reactive solvents such as acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methoxyethyl(meth)acrylate, phenoxyethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate etc. and benzene; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ether ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate: isopropyl ether, dioxane, and tetrahydro Organic solvents such as ethers such as 7ran; halogenated hydrocarbons such as methylene chloride, chloroform, trichloroethylene, and ethylene dichloride can be used.

The novel urethane (meth)acrylate prepolymer synthesized in this manner can be used in paints, adhesives, inks, hard coats, resists, and the like.

Further, the urethane (meth)acrylate prepolymer of the present invention may be an ethylenically unsaturated compound, various polymers (for example, unsaturated polyester).

Resins such as epoxy, polyamide, acrylic, and polyvinyl alcohol), organic solvents, fillers, tackifiers, stabilizers, plasticizers, leveling agents, dyes, pigments, etc. can be used in combination with the general formula (1 ) Urethane (meta) represented by
It can also be used in compositions based on acrylate prepolymers and ethylenically unsaturated compounds.

Ethylenically unsaturated compounds include styrene, α-methylstyrene, acrylonitrile, (meth)acrylamide, diacetone acrylamide, N-methyl(meth)acrylamide, N-methylol(meth)acrylamide, N-vinylpyrrolidone, diallyl phthalate, Alkyl (meth)acrylates such as allyl glycidyl ether, (meth)acrylic acid, methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, methoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, dibromopropyl (meth)acrylate, ) acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, ) acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)
Acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate,
Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trishydroxyethyl isocyanurate tri(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, hydrogenated bisphenol A Di(meth)acrylate, polyester(meth)acrylate obtained by the reaction of (meth)acrylic acid, glycols, and polybasic acid, epoxy(meth)acrylate obtained by the reaction of (meth)acrylic acid with an epoxy compound , urethane (meth)acrylate, dimethylaminoether (meth)acrylate obtained by the reaction of an isocyanate group-containing compound and hydroxyalkyl (meth)acrylate,
Examples include diethylaminoethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, silicone (meth)acrylate, amide (meth)acrylate, phosphoric acid (meth)acrylate, and the like.

These can be used alone or as a mixture.

The timing of blending the ethylenically unsaturated compound is particularly limited. In cases where the ethylenically unsaturated compound is used in cattle farms, it may be blended before the cretanization reaction. The amount of the ethylenically unsaturated compound is not particularly limited, but it is 99% by weight or less, preferably 90% by weight or less based on the total amount of the composition of the present invention.

The composition containing the urethane (meth)acrylate prepolymer and ethylenically unsaturated compound of the present invention as main components,
It can be applied or molded by means known to those skilled in the art, and it can be cured by means such as heat or radiation. For thermal curing, use a normal radical polymerization initiator,
For example, benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide, t-butyl perbenzoate. , azobisinbutyronitrile, etc. can be used, and if necessary, a radical polymerization accelerator, such as an organic metal salt such as cobalt octenoate, cobalt naphthenate, iron octenoate, manganese octenoate, vanadium octenoate, etc.
Organic amines such as N,N-dimethylaniline and the like can be used in combination. Radiation curing can be carried out using electron beams, ultraviolet rays, etc. In the case of ultraviolet curing, a normal photopolymerization initiator, and if necessary, a photopolymerization initiator and a sensitizer are used at 0.1
It is incorporated into the composition at a concentration of ~10% by weight. Examples of the photopolymerization initiator include benzoin alkyl ethers such as pentuine, hendiine isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, Michler's ketone, methyl-〇-benshii, and lupenzoate; acetophenone, trichloroacetophenone, 2 , 2-jethoxyacetophenone, p
- Acetophenones such as t-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, P-dimethylaminoacetophenone; xanthone, thioxanthone, 2-chlorothioxanthone, 2
- Thioxanthones such as isopropylthioxanthone: penzyl, 2-ethylanthraquinone, methyl-benzoylformate, 2-hydroxy-2-methyl-
1-phenylpropan-1-one, 2-hydroxy-4
'-Isopropyl-2-methylpropiophenone, 1-
Hydroxycyclohexylphenyl lactone.

Examples include tetramethylthiuram monosulfide and allyl diazonium salt, and examples of the sensitizer include amine compounds, sulfur compounds, and phosphorus compounds. These may be used alone or in combination. Furthermore, ultraviolet curing and thermosetting, or electron beam curing and thermosetting can also be used together.

〔Effect of the invention〕

The urethane (meth)acrylate prepolymer having the novel structure of the present invention can be polymerized to form a (co)polymer containing urethane bonds, or can be used as a coating material by curing a composition with an ethylenically unsaturated compound. glue,
It can be used in a wide range of applications such as inks, ultraviolet or electron beam curable resins, hard coats, resists, protective films for printed wiring boards, sealants, binders, and insulation boards.

Next, the present invention will be explained by examples, but the present invention is not limited by these examples. Note that parts in one example are parts by weight.

Reference Example 1 In a reaction vessel equipped with a thermometer and a stirrer, 232 parts of 2-hydroxyethyl acrylate, 0.07 part of hydroquinone monomethyl ether as a polymerization inhibitor, and 12- as a catalyst were placed in a reaction vessel equipped with a thermometer and a stirrer.
After adding 2.3 parts of tungstophosphoric acid, heat to 80℃ to 7.5
Holds time.

After the reaction is completed, adsorbent powdered magnesium silicate 12
After stirring at 40° C. for 30 minutes, purification was performed by pressure filtration, and the reaction product was a colorless transparent liquid (hereinafter referred to as hydroxyl group-containing acrylate oligomer (1)).

) 228 parts (yield: 98.3 parts) were obtained. IR, NMR,
From the GPC analysis results, the reaction product has an average molecular weight of 401.
was found to be a hydroxyl group-containing acrylate oligomer with the following structure.

Reference Example 2 After charging 260 parts of 2-hydroxypropyl acrylate, 0.08 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 26 parts of 12-tungstosilicic acid as a catalyst into the same reaction vessel as in Reference Example 1, the mixture was heated to 100°C for 5 hours. I kept it. After the reaction was completed, 13 parts of powdered basic magnesium aluminum hydroxy carbonate hydrate as an adsorbent was added, stirred at 60°C for 30 minutes, and purified by pressure-filtering to obtain a colorless transparent liquid. 251 parts (yield: 96.5 parts) of a reaction product (hereinafter referred to as hydroxyl group-containing acrylate oligomer (2)) were obtained.

The reaction product was a hydroxyl group-containing acrylate oligomer having an average molecular weight of 510 and the following structure.

Reference Example 3 After charging 232 parts of 2-hydroxyethyl acrylate, 0.07 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 4.6 parts of tungstosilicic acid as a catalyst into the same reaction vessel as in Reference Example 1, the temperature was maintained at 80°C for KIO time. did. After the reaction is complete, adsorbent powdered magnesium silicate 1
After adding 2 parts and stirring at 40°C for 30 minutes, purification was performed by pressure filtration to obtain 227 parts of a colorless transparent liquid reaction product (hereinafter referred to as hydroxyl group-containing acrylate oligomer (3)) (yield 97.8chi) was obtained. The reaction product was a hydroxyl group-containing acrylate oligomer having an average molecular weight of 1098 and having the following structure.

Reference Example 4 Into a reaction vessel similar to Reference Example 1, 260 parts of 2-hydroxyethyl methacrylate, 0.13 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.6 parts of tungstophosphoric acid as a catalyst were charged, and then heated to 100°C. It lasted for 4 hours. After the reaction was completed, 260 parts of water was added and the mixture was stirred at room temperature and left to stand.

When the residual liquid obtained by removing the aqueous layer (upper layer) is kept at 80°C for 30 minutes under a reduced pressure of 35 ol HH, water and a portion of the remaining raw materials are removed, resulting in a reaction of a colorless transparent liquid. 102 parts (yield: 39.2 parts) of a product (hereinafter referred to as hydroxyl group-containing methacrylate oligomer (4)) were obtained. The reaction product was a hydroxyl group-containing methacrylate oligomer having an average molecular weight of 297 and the following structure.

Example 1 Into a reaction vessel equipped with a thermometer, dropping funnel, reflux tube, and stirrer, 201 parts (0.5 equivalents) of the hydroxyl group-containing acrylate oligomer (1) obtained in Reference Example 1, and hydroquinone monomethyl as a polymerization inhibitor were added. 0.025 part of ether, dibutyltin dilaure as urethanization reaction catalyst)
0.13 parts of trimethylhexamethylene diisocyanate (manufactured by Hüls) was added under stirring.
, 5 equivalents) was added dropwise over 1 hour while cooling so that the temperature did not exceed 60°C. By maintaining the temperature at 60 to 65°C for an additional 4 hours, 254 parts of a reaction product (hereinafter referred to as urethane acrylate prepolymer (1)) was obtained.

The reaction product was found to be a urethane acrylate prepolymer having the following structure, based on the free incyanate group content (less than 0.1%) and the infrared absorption spectrum.

(However, C, H, indicate the residual amount of trimethylhexamethylene diisocyanate.) The infrared absorption spectrum of one reaction product is shown in FIG.

Example 2 In a reaction vessel similar to Example 1, 201 parts of the hydroxyl group-containing acrylate oligomer (1) obtained in Reference Example 1 (
0.5 equivalent), 0.029 part of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.14 part of diptertin dilauret as a rethanization reaction catalyst, and then 87 parts of 294-) lylene diisocyanate were added under stirring. (1 equivalent) was added dropwise over 2 hours while cooling so that the temperature did not exceed 60°C. By maintaining the temperature at 60 to 65°C for an additional 4 hours, 288 parts of a reaction product (hereinafter referred to as urethane acrylate prepolymer (2)) was obtained. From the free isocyanate group content (7.2%) and infrared absorption spectrum of the reaction product, it was found that the reaction product was a urethane acrylate prepolymer having the following structure.

(However, C, H, represent residues of 2.4-tolylene diisocyanate.) The infrared absorption spectrum of the reaction product is shown in FIG.

Example 3 After charging 288 parts of the urethane acrylate prepolymer <2) obtained in Example 2 to the same reaction vessel as in Example 1, 58 parts (0.5 equivalents) of 2-hydroxyethyl acrylate was added with stirring. The mixture was added dropwise over 2 hours while cooling so that the temperature did not exceed 60°C. Another 4 hours 60-65
By maintaining the temperature at .degree. C., 346 parts of a reaction product (hereinafter referred to as urethane acrylate prepolymer (3)) was obtained. Free isocyanate group content of the reaction product (0,1
rlb or less) and infrared absorption spectrum, it was found that the reaction product was a urethane acrylate prepolymer having the following structure.

(However, C, H, represents a residue of 2.4-) lylene diisocyanate. ) The infrared absorption spectrum of the reaction product is shown in FIG.

Example 4 Into the same reaction vessel as in Example 1, 122 parts (00 g equivalent) of polymethylene polyphenylisocyanate (Millionate MR-100, manufactured by Nippon Polyurethane Co., Ltd.) was charged, and while stirring, the hydroxyl group obtained in Reference Example 1 was added. Contains 120 parts (0.3 equivalents) of acrylate oligomer (1), 0 hydroquinone monomethyl ether as a polymerization inhibitor
．． A mixture consisting of 14 parts of dibutyltin dilaurate and 0.14 parts of dibutyltin dilaurate as a urethanization reaction catalyst was heated at 65°C.
After dropping at 60 to 65'C for 1 hour. Next, 35 parts of 2-hydroxyethyl acrylate (
0.3 equivalent) was added dropwise at 65°C for 1 hour, and then
1 reaction product (
Hereinafter, it will be referred to as urethane acrylate prepolymer (4). ) 277 copies were obtained. The free isocyanate group content of the reaction product was 4.5. The infrared absorption spectrum of the reaction product is shown in FIG.

Examples 5 to 11 According to the same procedure as in Example 1, reactions were carried out using the raw materials shown in Table 1 to obtain urethane (meth)acrylate prepolymers (5) to (11).

show.

Examples 12 to 22 0.01 part of hydroquinone monomethyl ether and benzyl dimethyl ketal were added to 100 parts of the mixture of the urethane (meth)acrylate prepolymers obtained in Examples 1 to 11 and the ethylenically unsaturated compounds shown in Table 2. (manufactured by Ciba Geigy, Irgacure 651) was added to prepare a photocurable composition Q3-a. This composition was applied to a thickness of 15μ on a steel plate panel and irradiated with an 80W/cIIL high-pressure mercury lamp from a distance of 10cIfL while moving the panel at a conveyor speed of 6m/min. Although 3 times of irradiation was required to obtain a cured coating film for only one example, a tack-free cured coating film was obtained with one irradiation for all other cases. The performance of the obtained cured coating film is shown in Table 2.

Example 23 100 parts of urethane acrylate prepolymer (1) obtained in Example 1 and 3 parts of methyl ethyl ketone peroxide
1 part and 1 part of cobalt naphthenate were added thereto, and the mixture was left to stand. After 24 hours, a strong cured resin with a pencil hardness of 5H was obtained.

Comparative Example 1 In a reaction vessel similar to Example 1, 116 parts (1 equivalent) of 2-hydroxyethyl acrylate, 0.029 part of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.14 part of dibutyltin dilaure as a urethanization catalyst were placed. After charging, 87 parts (1 equivalent) of 2.4-)lylene diisocyanate was added dropwise over 2 hours while stirring and cooling so that the temperature did not exceed 60°C. Another 8 hours 60-6
By maintaining the temperature at 5°C, the reaction product (hereinafter referred to as comparative urethane acrylate prepolymer (1)) 20
I got 3 copies. The free incyanate group content of the reaction product was below 0.1.

The viscosities (25°C, B-type viscometer) of the urethane acrylate prepolymer (3) obtained in Example 3 and Comparative Example 1 and the comparative urethane acrylate prepolymer (1) are shown below. It was found that the meth)acrylate prepolymer has low viscosity and excellent viscosity properties.

Table 2 PFtA: Phenoxy ether acrylate HDD: 1,6-hexanediol diacrylate DPHA Nidipentaerythritol hexaacrylate NVP: N-vinylpyrrolidone PETA Niventaerythritol tetraaphate (Note 2) JI8 K 540G method Gopan eye 1
Cut out 00 pieces, press the cellophane tag, peel it off vigorously, observe the peeling state of the goblets, 100 - (number of peeled goblets) / 100
It was displayed in

[Brief explanation of the drawing]

Figure 1 shows the infrared absorption spectrum of the urethane acrylate prepolymer (1) obtained in Example 1, and Figure 2 shows the infrared absorption spectrum of the urethane acrylate prepolymer (2) obtained in Example 2. FIG. 3 is an infrared absorption spectrum diagram of the urethane acrylate ligated vmer (3) obtained in Example 3, and FIG. 4 is an infrared absorption spectrum diagram of the urethane acrylate prepolymer obtained in Example 4. (4), and FIG. 5 shows the infrared absorption spectrum of Frethane methacrylate prepolymer (9) obtained in Example 9.
This is the infrared absorption spectrum of

Claims (1)

[Claims] 1. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.▼ [I] [However, in the formula, R^1 is a hydrogen atom or a methyl group, and they may be the same or different. Z is a divalent organic group having 2 to 20 carbon atoms and may be the same or different, p is an integer of 1 to 100, and R^2 is a hydroxyl group. It is a residue of a group-containing organic compound (excluding the hydroxyl group-containing (meth)acrylate oligomer represented by the following general formula [II]), and l
is an integer of 1 to 6, m is 0 or an integer of 1 to 5, n is 0 or an integer of 1 to 5, and l+m+n is 1
It is an integer of ~6, and Y is a (l+m+n)-valent isocyanate group-containing organic compound residue. ] Urethane (meth)acrylate prepolymer represented by (Note) ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] (However, in the formula, R^1 is a hydrogen atom or a methyl group, which may be the same or different, and Z is a carbon Hydroxyl group-containing (meth)acrylate oligomer 2 represented by (2 to 20 divalent organic groups, each of which may be the same or different, and p is an integer of 1 to 100); The urethane (meth)acrylate prepolymer according to claim 1, wherein m is 0. 3, Z is a divalent organic group having 2 to 6 carbon atoms, and p is 1 to 6.
20, l is an integer of 1 to 4, n is 0 or an integer of 1 to 3, and l+n is an integer of 1 to 4, the urethane (meth) according to claim 2. Acrylate prepolymer. 4, Z is a divalent organic group having 2 to 6 carbon atoms, and p is 1 to
is an integer of 20, l is an integer of 1 to 3, and m is an integer of 1 to 3.
is an integer of 3, n is 0 or an integer of 1 to 2, and l
The urethane (meth)acrylate prepolymer according to claim 1, wherein +m+n is an integer of 2 to 4. 5. The urethane (meth)acrylate prepolymer according to claim 3 or 4, wherein R^1 is a hydrogen atom. 6. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (However, in the formula, R^1 is a hydrogen atom or a methyl group, and they may be the same or different. , Z are divalent organic groups having 2 to 20 carbon atoms, and may be the same or different, and p is an integer of 1 to 100. Acrylate oligomer (A), general formula Y-(NCO)_l+m+n
(In the formula, Y is a residue of a (l+m+n)-valent isocyanate group-containing organic compound, and l+m+n is an integer of 1 to 6.) and, if necessary, the above-mentioned general General formula [I] characterized by reacting a hydroxyl group-containing organic compound (C) other than the hydroxyl group-containing (meth)acrylate oligomer (A) represented by formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼[I] [In the formula, R^1 is a hydrogen atom or a methyl group, which may be the same or different, and Z is a divalent organic group having 2 to 20 carbon atoms, and each They may be the same or different, p is an integer from 1 to 100, and R^2 is a hydroxyl group-containing organic compound (however, a hydroxyl group-containing (meth)acrylate represented by the above general formula [II]) (excluding oligomers), and l
is an integer of 1 to 6, m is 0 or an integer of 1 to 5, n is 0 or an integer of 1 to 5, and l+m+n is 1
It is an integer of ~6, and Y is a (l+m+n)-valent isocyanate group-containing organic compound residue. ] A method for producing a urethane (meth)acrylate prepolymer represented by: 7. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [However, in the formula, R^1 is a hydrogen atom or a methyl group, which may be the same or different, Z is a divalent organic group having 2 to 20 carbon atoms and may be the same or different, p is an integer of 1 to 100, and R^2 is a hydroxyl group-containing organic compound (however, (excluding hydroxyl group-containing (meth)acrylate oligomers represented by the following general formula [II]), and l
is an integer of 1 to 6, m is 0 or an integer of 1 to 5, n is 0 or an integer of 1 to 5, and l+m+n is 1
It is an integer of ˜6, and Y is a (l+m+n)-valent isocyanate group-containing organic compound residue. ] A composition whose main components are a urethane (meth)acrylate prepolymer represented by the following and an ethylenically unsaturated compound. (Note) ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] (However, in the formula, R^1 is a hydrogen atom or a methyl group, which may be the same or different, and Z is a carbon Hydroxyl group-containing (meth)acrylate oligomer 8, which is a divalent organic group of number 2 to 20, each of which may be the same or different, and p is an integer of 1 to 100. 8. The composition according to claim 7, wherein the ethylenically unsaturated compound is a (meth)acryloyl group-containing compound.