JPH10120745A - Activated radiation-curable resin composition - Google Patents

Abstract

(57) [Summary] [Problem] Liquid curing that is cured by actinic radiation such as ultraviolet rays, has a large tensile modulus, a large elongation at break, and a small dielectric constant, and is suitable as a protective coating material for high-frequency transmission components. To provide a mold resin composition. SOLUTION: (A) a urethane (meth) acrylate compound having an organic group such as an alkylene group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group, or a polysiloxane group; (B) two or more unsaturated bonding groups An alicyclic or heterocyclic compound having
An actinic radiation-curable resin composition comprising (C) an alicyclic compound having one unsaturated bond group and (D) a polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an actinic radiation-curable resin composition. More specifically, the present invention relates to a low dielectric constant urethane acrylate-based curable resin composition suitable as a wiring material, an insulating material, and the like for electronic devices.

[0002]

2. Description of the Related Art In recent years, in the production of electronic parts, ultraviolet curable materials have been favorably used as insulating and protective coating materials in order to enhance productivity. For example, unsaturated polyester resin, unsaturated epoxy ester resin and the like are used. However, these resins have a large dielectric loss factor and are not suitable for high-frequency transmission components. It is also known that an ultraviolet-curable resin containing hydrogenated 1,2-polybutadiene having a (meth) acryloyl group as a main component can be used as a low dielectric constant material for producing an enameled wire or the like (Japanese Patent Application Laid-open No. Hei 6-1994). However, the toughness was insufficient.

[0003]

An object of the present invention is to provide a novel actinic radiation curable resin composition.
Another object of the present invention is to cure with an actinic radiation such as ultraviolet rays, to have a large tensile modulus, a large elongation at break, a small dielectric constant, and a liquid curing type suitable for a protective coating material for a high-frequency transmission component. It is to provide a resin composition. Still other objects and advantages of the present invention will be apparent from the following description.

[0004]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) The following organic groups (a) to
A urethane (meth) acrylate compound having (e),
(A) a first organic group (V) having a (meth) acryloyl group at the terminal of the molecule, (b) a second organic group (Y) having an alicyclic structure having 6 to 20 carbon atoms, (c) A third organic group (E) selected from the group consisting of an alkylene group having 2 to 4 carbon atoms and a polyalkylene ether group having 2 to 4 carbon atoms and 2 to 10 repetitions (wherein a silicone group and a (meth) acrylate group) Is not directly bonded to), (d) the following formula

[0005]

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(R ¹ is a methyl group or an aromatic group; c is a number from 1 to 200; R ² and R ³ are each independently an alkyl group having 2 to 10 carbon atoms; Is a number from 0 to 10, provided that 2c + 4 R
70% by mole or more of ¹ is a methyl group, and a + b is 0 to 1
Number of 0. ) A fourth organic group (G), (e)
Urethane bond (U), (B) alicyclic or heterocyclic compound having two or more unsaturated bonding groups, (C) alicyclic compound having one unsaturated bonding group, and (D) polymerization initiator This is achieved by an actinic radiation curable resin composition characterized by containing:

Hereinafter, the actinic radiation-curable resin composition of the present invention will be described in detail. The urethane (meth) acrylate compound as the component (A) is as described above in (a)
To (e). The first organic group (V) having a (meth) acryloyl group at a molecular terminal is a group represented by the following structure. CH ₂ ＣＲCR ⁰¹ —COO—R ⁰² — where R ⁰¹ is hydrogen or a methyl group, and R ⁰² is 35 carbon atoms.
The following organic groups, an alkylene group, an aryl group,

[0008]

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Here, R ⁰³ is a group selected from H, —CH ₃ and a monovalent organic group, R ⁰⁴ and R ⁰⁵ are alkylene groups having 2 to 6 carbon atoms, and n is an integer of 1 to 5. Preferred examples of the R ⁰² is as follows.

[0010]

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A second compound having an alicyclic structure having 6 to 20 carbon atoms;
Is derived from, for example, a diisocyanate having a corresponding alicyclic structure. The second organic group (Y) is
It is preferably a divalent organic group having an isophorone structure. An alkylene group having 2 to 4 carbon atoms and 2 to 4 carbon atoms,
The third organic group (E) comprising a (poly) alkylene oxide group having 2 to 10 repetitions is not directly bonded to the silicone group, and is, for example, an alkylene glycol having 2 to 4 carbon atoms or a 2 to 4 carbon atoms. 4. Derived from a polyalkylene ether diol having 2 to 10 repetitions. That is, the third
Is a residue of an alkylene glycol compound generated when the alkylene glycol compound is reacted with an isocyanate compound, and is an alkylene group having 2 to 4 carbon atoms or a carbon atom having 2 to 4 carbon atoms in a repeating portion. polyalkylene ether residue of _{- (C n H 2n -O-)} m - is a (n =
2-4, m = 2-10). "The organic group (E) is not directly bonded to the silicone group and the (meth) acrylate group" means that the organic group (E) is included in the first and fourth organic groups. The alkylene ether residue means another organic group. Both ends of the organic group (E) are bonded to an adjacent organic group via a urethane bond.

The fourth organic group is derived, for example, from a polysiloxane diol having a corresponding structure. That is, the fourth
More specifically, the organic group (G) is a dialkylpolysiloxane having hydroxyl groups at both ends and having a molecular weight of 800 to 20,
000 is a residue of a dialkylpolysiloxane compound generated when a compound consisting of 000 is reacted with an isocyanate compound. In other words, the organic group (G) is a divalent organic group having a chemical structure obtained by removing -OH at both ends from a dialkylpolysiloxane having -OH groups at both ends.
In the above formula representing the fourth organic group (G), c is preferably 5 to 150, R ² and R ³ are each independently of each other, preferably an alkylene group having 2 to 4 carbon atoms, and a is Preferably, 1 and b are preferably 0. R ¹ is preferably all methyl groups. The urethane bond is generated by, for example, a reaction between a diisocyanate and a compound having a hydroxyl group.

The component (A) is preferably the above (a) to
The first to fourth organic groups in (d) may be in the above-mentioned (e) in any order.
Are bonded by a urethane bond. The compound of the component (A) preferably has the following structure. V-U-Y-U-[-EU-U-U-G-U-Y-U-] _m- V (wherein m is a number from 1 to 10, V, U, Y, E and G are the aforementioned organic groups.) The compound of component (A) is, for example, a diol having a polysiloxane structure, an alkylene glycol having 2 to 4 carbon atoms, or an alkylene group having 2 to 2 carbon atoms. 4, a polyalkylene ether diol, a diisocyanate having an alicyclic structure, and a (meth) acrylate having a hydroxyl group. Specific examples include the following production methods 1 to 3.

Production method 1: nmol of a diol having a polysiloxane structure (n is an integer of 1 to 10, preferably n is 3 to 5) and alkylene glycol or alkylene glycol having 2 to 4 carbon atoms The group has 2 carbon atoms
And 4 moles of a polyalkylene ether diol,
A method in which (2n + 1) moles of diisocyanate having an alicyclic structure are simultaneously reacted, and an isocyanate group of an obtained intermediate product is reacted with 2 moles of (meth) acrylate having a hydroxyl group.

Production method 2: diisocyanate (2n + 1) mol having an alicyclic structure and (meth) having a hydroxyl group
A mixture of a monoisocyanate compound having a (meth) acryloyl group and an unreacted diisocyanate obtained by reacting 2 mol of an acrylate is mixed with nmol of a diol having a polysiloxane structure and an alkylene glycol having 2 to 4 carbon atoms or an alkylene group. Has 2 carbon atoms
To 4 moles of the polyalkylene ether diol. Production method 3: Diisocyanate having an alicyclic structure (2n
+1) mol, diol n having a polysiloxane structure
A method in which an alkylene glycol having 2 to 4 carbon atoms or a polyalkylene ether diol having 2 to 4 carbon atoms in an alkylene group and 2 moles of a hydroxyl group-containing (meth) acrylate are simultaneously reacted.

In the reactions of the above production methods 1 to 3, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine,
A urethane-forming catalyst such as triethylenediamine or 2-methyltriethylenediamine is used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of the reactants. The reaction is preferably carried out at a temperature of usually 10 to 90 ° C, particularly preferably 30 to 80 ° C. Although the production of the component (A) is possible without a solvent,
It is preferable to perform the reaction in the presence of a solvent from the viewpoint of reaction control. It is necessary that the solvent does not have a functional group that reacts with an isocyanate group such as a hydroxyl group. In order to omit the step of removing or replacing the solvent after the reaction, other components used in the composition of the present invention, for example, a part or all of the components (B) and (C) can be used as the solvent. .
In this case, it is necessary to manufacture the component (A) under such a condition that the components (B) and (C) do not undergo a polymerization reaction or the like. Examples of the polysiloxane in the diol having a polysiloxane structure used in the above method include the following formula (2).

[0017]

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In the formula, R ¹ is a methyl group or an aromatic group, c is a number of 1 to 200, R ² and R ³ are each independently an alkyl group having 2 to 10 carbon atoms, a and b are each a number from 0 to 10; However, 70 mol% or more of 2c + 4 R ¹ is a methyl group, and a +
b is a number from 0 to 10, preferably a = 1, b = 0, and R ¹ is a methyl group. Examples of diols having these polysiloxane structures include the following in formula (2) wherein R ¹ is a methyl group, R ² is an ethylene group, R ³ is a propylene group, a is 1 and b is 0. . FM-4411, F
M4421, FM4425 (all manufactured by Chisso Corporation),
X-22-160AS, KF6001, KF-600
2. KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.).
Each number average molecular weight is FM-4411, X-22
-160AS is about 1000, KF6001 is about 200
0, KF6002 about 3000, FM4421 about 50
00, KF6003 is about 5600, FM4425 is about 1
It is 0,000. Among these diols having a polysiloxane structure, FM4411, X-22-160A
S and KF6001 are preferable, and FM4411 and KF6001 are particularly preferable. These diols having a polysiloxane structure can be used alone or in combination of two or more.

Examples of the alkylene glycol having 2 to 4 carbon atoms or the polyalkylene ether diol having 2 to 4 carbon atoms in the alkylene group include ethylene glycol, propylene glycol, isopropylene glycol, tetramethylene glycol, diethylene glycol, and polyethylene. Glycol, polypropylene glycol, polytetramethylene glycol and the like.
Of these, ethylene glycol, propylene glycol, diethylene glycol and the like are preferred, and particularly preferred are ethylene glycol and propylene glycol. These alkylene glycols having 2 to 4 carbon atoms or polyalkylene ether diols having 2 to 4 carbon atoms in the alkylene group can be used alone or in combination of two or more. Specific examples of the diisocyanate having an alicyclic structure include isophorone diisocyanate, cyclohexane 1,4-diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated naphthalene diisocyanate, hydrogenated bisphenol A diisocyanate, and hydrogenated xylylene diisocyanate. And isocyanate. Of these, isophorone diisocyanate is preferred. These diisocyanates having an alicyclic structure can be used alone or in combination of two or more.

The (meth) acrylate having a hydroxyl group is a (meth) acrylate ester having a hydroxyl group, for example, a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate. Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tripenta ( (Meth) acrylate, 1,4-butanediol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate Neopentyl glycol mono (meth) acrylate, glycerin di (meth) acrylate, represented by the following formula (3) and (4) (meth)
Acrylates, as well as alkyl glycidyl ethers,
Compounds obtained by the addition reaction of a glycidyl group-containing compound such as aryl glycidyl ether and glycidyl (meth) acrylate with (meth) acrylic acid can be mentioned.

[0021]

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(Wherein, R ⁴ represents a hydrogen atom or a methyl group)

[0023]

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Wherein R ⁴ is as defined above, and p is 1
~ 5)

Preferred among these are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and (meth) acrylates represented by the above formulas (3) and (4). Can be These (meth) acrylates having a hydroxyl group can be used alone or in combination of two or more. The component (A) thus obtained is preferably contained in the composition of the present invention in an amount of preferably 10%.
-55% by weight, more preferably 15-
It is contained in a proportion of 50% by weight. If it is less than 10% by weight, the elongation at break of the cured product tends to be small, and if it exceeds 55% by weight, the tensile modulus of the cured product tends to be small, and it is difficult to use the composition of the present invention for high-frequency transmission parts, which is the main application. .

The alicyclic or heterocyclic compound having at least two unsaturated bond groups, which is the component (B) used in the present invention, has an unsaturated bond group in one molecule, preferably 2-4. And more preferably two. Here, examples of the unsaturated bonding group include a (meth) acryloyl group, a vinyl ether group, and a vinyl group. Of these, preferred are (meth) acryloyl groups and the like. The alicyclic structure in the alicyclic compound having at least two or more unsaturated bond groups has 4 to 4 carbon atoms.
An alicyclic hydrocarbon group having 18 to 18 rings is preferable. Examples of such compounds include cyclohexyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the following formulas (5), ( And the like. Preferred compounds include tricyclodecane dimethanol diacrylate.

[0027]

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In the formula, R ⁴ represents a hydrogen atom or a methyl group,
R5 represents an alkylene group having 2 to 8, preferably 2 to ⁵ carbon atoms, and p1, p2 and p3 each independently represent an integer of 0 to 8, preferably 1 to 4.

[0029]

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In the formula, R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ is 2 to 8 carbon atoms, preferably 2-5 alkylene group, is q1 and q2 0 to 8, preferably an integer of 1-4.

The heterocyclic structure of the heterocyclic compound having at least two or more unsaturated bond groups has 1 to 4 oxygen atoms, nitrogen atoms and the like, and has 2 to 2 carbon atoms.
Groups having 4 are preferred. Examples of the cyclic structure of the heterocyclic structure include an aromatic ring and an alicyclic ring, and an alicyclic structure is preferable. Such compounds include the following formula (7):
Compounds represented by (8) or (9) are mentioned. Preferred compounds include compounds represented by the following formula (7).

[0032]

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In the formula, R ⁷ and R ⁸ represent a hydrogen atom or a methyl group, R ⁹ represents an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, and r represents 0 to 8, preferably 0 to 4 Indicates an integer.

[0034]

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In the formula, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are a hydrogen atom or a methyl group, R ¹⁴ is an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, and s1 and s2 are 1 to 8,
It preferably represents an integer of 1 to 4.

[0036]

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In the formula, R ¹⁵ represents a hydrogen atom or a methyl group,
R ¹⁶ represents an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, and t1 and t2 each represent an integer of 1 to 8, preferably 1 to 4.

The alicyclic or heterocyclic compound having two or more unsaturated bonding groups as the component (B) can be used alone or in combination of two or more. The alicyclic or heterocyclic compound having at least two or more unsaturated bonding groups is preferably contained in the composition of the present invention in a proportion of 5 to 40% by weight, more preferably 10 to 30% by weight. It is contained in the ratio of.

The alicyclic compound having one unsaturated bond, which is the component (C) used in the present invention, has one unsaturated bond in one molecule. Here, examples of the unsaturated bonding group include a (meth) acryloyl group, a vinyl ether group, and a vinyl group. Of these, preferred are (meth) acryloyl groups and the like. As this alicyclic compound, an alicyclic hydrocarbon group having 1 to 3 rings having 4 to 18 carbon atoms is preferable. Such compounds include, for example, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, and the like. Preferred compounds include isobornyl acrylate.

The alicyclic compound having one unsaturated bonding group as the component (C) can be used alone or in combination of two or more. The alicyclic compound having one unsaturated bond group is preferably present in the composition of the present invention in an amount of from 20 to
70% by weight, more preferably 30 to 6%.
It is contained at a ratio of 5% by weight. The compositions of the present invention are cured by actinic radiation. Here, the actinic radiation is radiation exhibiting a chemically active action, and specifically, infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays
Line, γ-ray, etc. Of these, ultraviolet rays can be particularly preferably used. The polymerization initiator, which is the component (D) used in the present invention, is a component necessary for curing the composition of the present invention by irradiating it with actinic radiation.

When the composition of the present invention is cured with, for example, ultraviolet light, a photopolymerization initiator is used. Examples of such a photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4
-Chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-
Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl) -butan-1-one, 1
-[4- (2-hydroxyethoxy) -phenyl] -2
-Hydroxy-2-methyl-1-propan-1-one,
Commercially available products such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide include Irgacure 18
4, 651, 500, 907, 369, 2959, CG
I-784, CGI-1700 (all, manufactured by Ciba-Geigy), Lucirine TPO, Initiator 654 (all, B
ASF), Darocure 1116, 1173, 426
5 (all manufactured by Merck), Jubecryl P36 (UCB) and the like.

Of these, benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone,
Thioxanthone, Irgacure 184, 651, 907,
369, CGI-1700 (Ciba-Geigy), Lucirine TPO, Initiator 654 (B,
ASF), Darocure 1116, 1173 (above,
Merck), Ubecryl P36 (UCB) and the like are used. The polymerization initiator (D) is usually used in an amount of 0.05 based on 100 parts by weight of the total of the components (A), (B) and (C).
To 25 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight.

When a photopolymerization initiator is used, a photosensitizer can be used in combination. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Isoamyl and the like are commercially available as Ubecryl P102, 103, 104, 105 (above UCB
And the like). The composition of the present invention comprises the above (A)
The component, the component (B), the component (C) and the component (D) are essential, but if necessary, a reactive dilution curable with an active energy ray as long as the effect of the composition of the present invention is not impaired. Agents and other additives. The reactive diluent can be used in the composition in an amount of 0 to 40% by weight, that is, not used: 0% by weight or within 40% by weight. If it exceeds 40% by weight, the dielectric constant becomes large, which is not preferable.

The reactive diluent includes the component (B),
A monofunctional compound and a polyfunctional compound other than the component (C) are included. Examples of the monofunctional compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, and ethyl.
(Meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl
(Meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (Meta)
Acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth)
Acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene Glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth)
Acrylate, methoxypolypropylene glycol (meth) acrylate, tricyclodecanyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, (meth) acryloylmorpholine, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, maleic esters, fumaric esters and the following formula (1)
0) to (12).

[0045]

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In the formula, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents an alkylene group having 2 to 6, preferably 2 to 4 carbon atoms, and R ²³ represents a hydrogen atom or 1 to 12 carbon atoms, preferably Represents an alkyl group of 1 to 9, and u represents an integer of 0 to 12, preferably 1 to 8.

[0047]

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In the formula, R ²¹ is as described above, R ²⁴ is an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, and v is an integer of 1 to 8, preferably 1 to 4. .

[0049]

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In the formula, R ²¹ , R ²⁴ and v are as described above, and R ²⁵ represents a hydrogen atom or a methyl group.

As the monofunctional compound of the reactive diluent, Alonix M-111 and M-1 are commercially available.
13, M-114, M-117 (Toa Gosei Co., Ltd.)
KAYARAD TC110S, R-629, R-644
(Nippon Kayaku Co., Ltd.) and Viscoat 3700 (Osaka Organic Chemical Industry Co., Ltd.) can be easily obtained.
Examples of the polyfunctional compound include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) Acrylate, 1,4-butanediol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, epoxy obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A (Meth) acrylate, triethylene glycol divinyl ether and the like. Commercially available products include Yupimer UV SA2007 (manufactured by Mitsubishi Chemical Corporation), Viscoat 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and KAYARAD H
DDA, DPCA-20, -30, -60, -120,
HX-620, D-310, D-330 (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-21
5, M-315, M-325 (Toa Gosei Co., Ltd.)
Manufactured) can be easily obtained.

These reaction diluents can be used alone or in combination of two or more. Further, as other additives that can be added to the composition of the present invention, epoxy resin, polyamide, polyamide imide, polyurethane,
Polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene /
Styrene block copolymer, styrene / ethylene / butene / styrene block copolymer, styrene / isoprene / styrene block copolymer, petroleum resin, xylene resin, ketone resin, fluorine oligomer, silicone oligomer, polysulfide oligomer, etc. No.

Further, the composition of the present invention may contain various additives other than those described above, such as antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, antioxidants, thermal polymerization inhibitors, leveling agents, Coloring agents, surfactants, storage stabilizers,
A plasticizer, a lubricant, a solvent, a filler, an antioxidant, a wettability improver, a coating surface improver, and the like can be added as necessary. Here, commercially available antioxidants include Irganox 1
010, 1035, 1076, 1222 (all manufactured by Ciba-Geigy). As an ultraviolet absorber,
Tinuvin P, 234, 320, 326, 327, 32
8, 213 (all manufactured by Ciba-Geigy), Sumisorb 1
10, 130, 140, 220, 250, 300, 32
0, 340, 350, and 400 (all manufactured by Sumitomo Chemical Co., Ltd.). Commercially available light stabilizers include Tinuvin 292, 144, 622LD (all manufactured by Ciba Geigy) Sanol LS-770, 765, 29
2, 2626, 1114, 744 (Sankyo Chemical Industry Co., Ltd.)
Manufactured). As a silane coupling agent,
γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, commercially available products such as SH6
062, 6030 (manufactured by Toray Silicone Co., Ltd.), KB
E903, 603, 403 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. As a commercially available anti-aging agent, An
tigene W, S, P, 3C, 6C, RD-G, FR, A
W (above, manufactured by Sumitomo Chemical Co., Ltd.), Non-flex D
CD (Seiko Chemical Co., Ltd.), Nocrack DP, PA, C
D, AD-F (both manufactured by Ouchi Shinko Co., Ltd.) and the like.

For the purpose of further reducing the dielectric constant of the cured product of the composition of the present invention, a foaming agent that foams by heat or light can be dispersed and mixed into the composition to make the cured product a foamed structure. . Examples of the foaming agent to be used include a chemical foaming agent that generates a gas by heat or light, and a hollow particle that contains a volatile substance as a physical foaming agent and expands by heat. Alternatively, hollow particles containing a gas such as air, nitrogen, or argon may be dispersed and mixed in the composition to reduce the dielectric constant of the cured product. Examples of the chemical blowing agents mentioned here include sodium bicarbonate, ammonium bicarbonate, ammonium carbonate, N, N′-dinitrosopentamethylenetetramine, azodicarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), p-toluenesulfonyl hydrazide and the like. Specific examples of the physical foaming agent include hollow particles made of vinylidene chloride-based resin containing isobutane. The composition of the present invention can be produced by mixing the above-mentioned components by a conventional method. The viscosity of the composition of the present invention thus obtained is usually from 200 to 30,000.
0 cps / 25 ° C., preferably 300 to 10,000 c
ps / 25 ° C.

[0055]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the following, parts mean parts by weight. Urethane acrylate synthesis example 1 In a reaction vessel equipped with a stirrer, 400.0 g of isobornyl acrylate and 305.6 of isophorone diisocyanate were added.
g, silicone diol having a number average molecular weight of 1,000 (FM
625.6 g, 38.8 g of ethylene glycol, and 0.3 g of 2,6-di-tert-butyl-methylphenol as a polymerization inhibitor were charged. This was cooled to an internal temperature of 10 ° C. or lower in an ice water bath, and 0.8 g of dibutyltin dilaurate was added thereto to start the reaction. The reaction was carried out for 2 hours while maintaining the internal temperature at 20 to 35 ° C. The reaction was carried out for 2 hours while maintaining the temperature at 35 ° C to 45 ° C. Next, 29.0 g of hydroxyethyl acrylate was added, and stirring was continued at an internal temperature of 45 to 60 ° C. for 3 hours. Then, the reaction was terminated, and a urethane acrylate (A1) having a number average molecular weight of about 8,000 was obtained. The obtained urethane acrylate solution of isobornyl acrylate is referred to as oligomer (1). The weight ratio of urethane acrylate to isobornyl acrylate is 10: 4.

Urethane acrylate synthesis example 2 In a reaction vessel equipped with a stirrer, 400.0 g of isobornyl acrylate and 194.7 of isophorone diisocyanate were added.
g, silicone diol having a number average molecular weight of 2000 (KF
6001, manufactured by Shin-Etsu Chemical Co., Ltd.), 751.8 g, 23.3 g of ethylene glycol, and 0.3 g of 2,6-di-tert-butyl-methylphenol as a polymerization inhibitor were charged. This was cooled to an internal temperature of 10 ° C. or lower in an ice water bath, and 0.8 g of dibutyltin dilaurate was added thereto to start the reaction. The reaction was carried out for 2 hours while maintaining the internal temperature at 20 to 35 ° C. The reaction was carried out for 2 hours while maintaining the temperature at 35 ° C to 45 ° C. Next, hydroxyethyl acrylate was added to 29.1.
g was added and stirring was continued at an internal temperature of 45 to 60 ° C. for 3 hours. Then, the reaction was terminated, and a urethane acrylate (A2) having a number average molecular weight of about 8,000 was obtained. The resulting urethane acrylate solution in isobornyl acrylate is referred to as oligomer (2). The weight ratio of urethane acrylate to isobornyl acrylate is 10: 4.

Urethane acrylate synthesis example 3 In a reaction vessel equipped with a stirrer, 400.0 g of isobornyl acrylate and 264.6 of isophorone diisocyanate were added.
g, silicone diol having a number average molecular weight of 1,000 (FM
4411, manufactured by Chisso Corp.) 596.0 g, 0.3 g of 2,6-di-tert-butyl-methylphenol as a polymerization inhibitor
Was charged. This was cooled to an internal temperature of 10 ° C. or lower in an ice water bath, and 0.8 g of dibutyltin dilaurate was added thereto to start the reaction. The reaction was carried out for 2 hours while maintaining the internal temperature at 20 to 35 ° C. The reaction was carried out for 2 hours while maintaining the temperature at 35 ° C to 45 ° C. Next, 138.3 g of hydroxyethyl acrylate was added, and stirring was continued at an internal temperature of 45 to 60 ° C. for 3 hours. Then, the reaction was terminated, and the number average molecular weight was reduced to about 1
700 urethane acrylates (A3) were obtained. The resulting urethane acrylate solution in isobornyl acrylate is referred to as oligomer (3). The weight ratio of urethane acrylate to isobornyl acrylate is 10: 4.

Urethane acrylate synthesis example 4 In a reaction vessel equipped with a stirrer, 109.9 g of isobornyl acrylate and 66.46 of isophorone diisocyanate were placed.
g, silicone diol having a number average molecular weight of 5000 (FM
4421, manufactured by Chisso Corp.), 100.0 g, and 0.8 g of phenothiazine and 0.5 g of 2,6-di-tert-butyl-methylphenol as polymerization inhibitors. After cooling this in an ice water bath to a reaction vessel internal temperature of 10 ° C or less, 1.0 g of dibutyltin dilaurate was added thereto while maintaining the internal temperature at 20 to 30 ° C to start the reaction, and the internal temperature was raised to 40 to 50 ° C. The reaction was carried out for 1 hour while maintaining. Next, 23.2 g of hydroxyethyl acrylate was added, and stirring was continued at an internal temperature of 45 to 60 ° C. for 3 hours. Then, the reaction was terminated, and a urethane acrylate (A4) having a number average molecular weight of about 10,900 was obtained. The resulting urethane acrylate solution in isobornyl acrylate is referred to as oligomer (4). The weight ratio of urethane acrylate to isobornyl acrylate is 10:
It is one.

Urethane acrylate synthesis example 5 In a reaction vessel equipped with a stirrer, 400.0 g of isobornyl acrylate and 165.7 of isophorone diisocyanate were placed.
g, 746.6 g of polytetramethylene glycol having a number average molecular weight of 2,000, and 0.3 g of 2,6-di-tert-butyl-methylphenol as a polymerization inhibitor. This was cooled in an ice water bath to a temperature of 10 ° C. or less in the reaction vessel, and 0.8 g of dibutyltin dilaurate was added thereto to start a reaction.
The reaction was performed for 2 hours while maintaining the internal temperature at 20 to 35 ° C, and then the reaction was performed for 2 hours while maintaining the internal temperature at 35 ° C to 45 ° C. Next, 86.6 g of hydroxyethyl acrylate was added,
After continuing stirring at an internal temperature of 45 to 60 ° C. for 3 hours, the reaction was terminated, and a urethane acrylate (A5) having a number average molecular weight of about 2700 was obtained. The resulting urethane acrylate solution in isobornyl acrylate is referred to as oligomer (5). The weight ratio of urethane acrylate to isobornyl acrylate is 10: 4.

Example 1 In a reaction vessel equipped with a stirrer, 21.0 parts of oligomer (1) (component A) (A: 15 parts, C: 6 parts), tricyclodecane dimethanol diacrylate ( B component) 20.0 parts of trade name SA1002 (manufactured by Mitsubishi Chemical Corporation) and 6 parts of isobornyl acrylate (C component)
A reaction vessel equipped with 5.0 parts (including 6 parts of the component (C) from the oligomer (1)), 3.0 parts of Irgacure 184 as a photopolymerization initiator, and 0.3 parts of Irganox 1035 as an antioxidant. 50-60
The mixture was stirred and mixed at ℃ to obtain a transparent liquid composition (Formulation Example 1). Example 2 33.6 parts of oligomer (1) (A1: 24 parts, C: 9.6)
15.0 parts of the same B component as in Formulation Example 1 and 61.0 parts of the same C component as in Formulation Example 1 (including 9.6 parts of the component (C) from the oligomer (1)). A composition was obtained in the same manner as in Formulation Example 1 except for the above.

Example 3 42.0 parts of oligomer (1) (A: 30 parts, C: 12
Parts), 10.0 parts of the same B component as in Formulation Example 1 and 60.0 parts of the same C component as in Formulation Example 1 (including 12 parts of the component (C) from the oligomer (1)) Was obtained in the same manner as in Formulation Example 1. Example 4 53.2 parts of oligomer (1) (A1: 38 parts, C: 15.
2 parts), 20.0 parts of the same B component as in Formulation Example 1 and 42.0 parts of the same C component as in Formulation Example 1 (including 15.2 parts of the (C) component from the oligomer (1)). Except for using, a composition was obtained in the same manner as in Formulation Example 1.

Example 5 65.8 parts of oligomer (1) (consisting of 47 parts of A1 component and 18.8 parts of C component), 20.0 parts of the same B component as in Formulation Example 1
A composition was obtained in the same manner as in Formulation Example 1 except that 33.0 parts of the same C component as in Formulation Example 1 (including 18.8 parts of the component (C) from the oligomer (1)) were used. Example 6 44.8 parts of oligomer (2) (component A) (component A2 32.
0 parts, C component 12.8 parts), 10.0 parts of the same B component as in Formulation Example 1 and 58.0 of the same C component as in Formulation Example 1
A composition was obtained in the same manner as in Formulation Example 1, except that 1 part (including 12.8 parts of the component (C) from the oligomer (2)) was used.

Comparative Example 1 7.0 parts of oligomer (1) (5.0 parts of A1 component, 2 parts of C component)
Parts), 30.0 parts of the same B component as in Formulation Example 1 and 65.0 parts of the same C component as in Formulation Example 1 (including 2 parts of the (C) component from the oligomer (1)). Was obtained in the same manner as in Formulation Example 1. Comparative Example 2 95.0 parts of the oligomer (1) (consisting of 68 parts of the A1 component and 27 parts of the C component), 5.0 parts of the B component and 27 parts of the same C component as in the composition example 1 (the component from the oligomer (1)) ) Was obtained in the same manner as in Formulation Example 1 except that (1) was used.

Comparative Example 3 Oligomer (3) 42.0 parts (A3 component 30)
Parts, 12 parts of the C component), 25.0 parts of the same B component as in Formulation Example 1 and 45.0 parts of the same C component as in Formulation Example 1 (including 12 parts of the (C) component from the oligomer (3)) ) Was obtained in the same manner as in Formulation Example 1 except that (1) was used. Comparative Example 4 55.0 parts of oligomer (4) (component A) (component A4 50)
Part, C component 5 parts), the same B component 1 as in Formulation Example 1
1.5 parts, 30.0 parts of the same C component as in Formulation Example 1 (including 5 parts of the (C) component from the oligomer (4)), and 5.0 parts of N-vinylpyrrolidone as a reaction diluent Was obtained in the same manner as in Formulation Example 1. Comparative Example 5 53.2 parts of oligomer (5) (component A) (A5 component 38.
1 part, C component 15.1 parts), 25.0 parts of the same B component as in Formulation Example 1, and 36.9 parts of the same C component as Formulation Example 1.
A composition was obtained in the same manner as in Formulation Example 1 except for using parts (including 15.1 parts of the component (C) from the oligomer (5)).

Evaluation Test A test piece was prepared from the composition obtained above by the following method (1), and the dielectric constant, tensile modulus, and elongation at break were obtained by the following methods (2), (3) and (4). Was measured. Table 1 shows the results. (1) Preparation of test piece The composition was applied on a glass plate using an applicator bar having a thickness of 150 μm, and irradiated with 500 mJ / cm ² ultraviolet rays in a nitrogen atmosphere to obtain a cured film. Next, the cured film was peeled off from the glass plate, and 500 mJ / cm ² again from the glass surface of the peeled cured film.
Was irradiated in a nitrogen atmosphere. The cured film thus obtained was conditioned at 23 ° C. and a relative humidity of 50% for 24 hours to obtain a test piece. (2) Measurement of dielectric constant The cured film obtained in the above (1) was used as a test piece for HP41.
JIS K using a 94A impedance / gain fuse analyzer and HP16451B dielectric measurement electrode (all manufactured by Yokogawa-Hewlett-Packard Co., Ltd.)
The dielectric constant at a frequency of 1 MHz was measured according to 6911.

(3) Measurement of Tensile Modulus (Y ₂₃ ) at 23 ° C. The cured film obtained in the above (1) was used as a test piece according to JIS.
According to K7113, the tensile modulus was measured in a constant temperature and humidity room at 23 ° C. and a humidity of 50%. However, the pulling speed is 1mm
/ Min, and the tensile modulus was calculated from the tensile stress at 2.5% strain. (4) Measurement of Elongation at Break (TE ₂₃ ) at 23 ° C. The cured film obtained in the above (1) was tested on a test piece according to JIS K7.
According to 113, in a constant temperature / humidity room at a temperature of 23 ° C and a humidity of 50%, a tensile speed is 50 mm / min, and a distance between marked lines is 25 mm.
The elongation at break was measured under the following conditions.

[0067]

[Table 1]

As is clear from Table 1, all of the cured products of the compositions according to Examples 1 to 6 have high Young's modulus and high elongation at break, excellent mechanical properties, and a dielectric constant at 1 MHz of 3.0. The cured product obtained as low as below can be suitably used as a protective coating material for high-frequency transmission products. On the other hand, in Comparative Example 1, the component A was small, the elongation at break was as small as 15% or less, and the toughness was poor. In Comparative Example 2, the component A was large and the Young's modulus was as small as 30 kg / mm ² or less, so that sufficient strength as a protective coating material could not be obtained. Comparative Examples 3 and 4 use only silicone diol as the diol of component A and do not have a (poly) alkylene oxide group (E), but Comparative Example 3 has a small elongation at break, and Comparative Example 4 has a Young's modulus. Since it is small, sufficient strength and toughness cannot be obtained as a protective coating material. In Comparative Example 5, only polytetraethylene glycol was used as the diol of the component A, but the dielectric constant (1 MH)
z) is as high as 3.3 or more, and when used as a protective coating material for high-frequency transmission products, transmission loss increases, which is not preferable.

[0069]

According to the present invention, it is possible to obtain an active radiation-curable resin composition having a cured product having a low dielectric constant and sufficient tensile elasticity and toughness as a protective coating material for high-frequency transmission products.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Takeshi Watanabe 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd. (72) Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo No. Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] (A) a urethane (meth) acrylate compound having the following organic groups (a) to (e); (a) a first organic group (V) having a (meth) acryloyl group at a terminal of a molecule; (B) a second organic group (Y) having an alicyclic structure having 6 to 20 carbon atoms, (c) an alkylene group having 2 to 4 carbon atoms and a polyalkylene group having 2 to 4 carbon atoms and having 2 to 10 repetitions. Third organic group (E) selected from the group consisting of alkylene ether groups
(However, it is not directly bonded to the silicone group and the (meth) acrylate group), and (d) the following formula: (R ¹ is a methyl group or an aromatic group, and c is 1-2
And R ² and R ³ independently of each other have 2 to 2 carbon atoms.
A and b are each 0 to 1
0, provided that 2c + 4 70 mole% of R ¹
The above is a methyl group, and a + b is a number from 0 to 10. A) an alicyclic or heterocyclic compound having two or more unsaturated bonding groups, (C) one unsaturated group, An active energy ray-curable resin composition comprising an alicyclic compound having a bonding group and (D) a polymerization initiator.