JP2001302680A - Silicon-containing compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new silicon-containing compound having a radical polymerization initiating group and useful as a surface modifier for reactive particles used in a resin composition capable of forming a film (cured film) on the surfaces of various kinds of substrates. SOLUTION: This silicon-containing compound is represented by the following formula (1), (2) or (3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel silicon-containing compound and a method for producing the same. More specifically, a silicon-containing compound having a novel radical polymerization initiating group useful as a surface modifier for reactive particles used in a resin composition capable of forming a coating film (cured film) on the surface of various substrates, and its efficiency Production method. The resin composition using the reactive particles surface-modified with the silicon-containing compound of the present invention has excellent cured product productivity and, when formed into a cured product, has excellent high scratch resistance, high transparency, low It has curling properties and stain resistance.

[0002]

2. Description of the Related Art Hitherto, silane coupling agents have been used for chemically modifying the surface of inorganic fine particles, and the use of these surface-modified inorganic fine particles in various organic / inorganic composite materials has been attempted. .

[0003] For example, Japanese Patent Publication No. 62-21815 discloses a composition of acrylate and particles obtained by modifying the surface of colloidal silica with methacryloxysilane as a radiation (light) curable coating material. It has been proposed. This type of radiation-curable composition has recently been widely used because of its excellent cured product productivity. However, since the radiation-curable composition forms a cured film, usually by radical polymerization, there is a problem that the cured film obtained is not sufficiently cured due to the influence of dissolved oxygen in the atmosphere or in the polymerization system. there were.

[0004] As a means for solving the insufficient curing due to oxygen inhibition, there is a method of increasing the amount of a photo-radical initiator or using a photo-radical initiator which is less susceptible to oxygen inhibition. However, this method is not always satisfactory because the amount of the unreacted photoradical initiator in the cured product increases and adversely affects the coloring of the cured film and the decrease in scratch resistance.

[0005] As a method for solving this, use of a polymer initiator, introduction of an initiator into a crosslinking system, and the like are available. As an example, Japanese Patent Application Laid-Open No. 9-328522 discloses a photocuring method comprising a silica fine particle having a radical polymerization initiating group and an acrylic monomer in which an alkoxysilane compound having a radical polymerization initiating group at the terminal is reacted on the surface of the silica fine particle. A coating material is disclosed. However, even with this method, the problem of a decrease in the scratch resistance of the cured film could not be sufficiently solved.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made in view of the above-mentioned problems. The present invention relates to reactive particles used in a resin composition capable of forming a coating film (cured film) on the surface of various substrates. An object of the present invention is to provide a novel silicon-containing compound having a radical polymerization initiating group, which is useful as a surface modifier, and an efficient production method thereof. The resin composition using the reactive particles surface-modified with the silicon-containing compound of the present invention has excellent cured product productivity and, when formed into a cured product, has excellent high scratch resistance, high transparency, low It has curling properties and stain resistance.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found a novel compound having a radical polymerization initiating group in the chemical structure, which is useful as a surface modifier for reactive particles. The present inventors have found a silicon-containing compound and completed the present invention. That is, the present invention provides the following silicon-containing compound and a method for producing the same.

[1] A silicon-containing compound represented by the following formula (1), (2) or (3):

[0009]

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[0010]

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[0011]

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[2] The compound represented by the formula (2) is 2,2
The silicon-containing compound according to the above [1], which is a 4-form and / or a 2,6-form.

[3] A compound represented by the following formula (4) or (5), isophorone diisocyanate, 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate, and a compound represented by the following formula (6) The method for producing a silicon-containing compound according to the above [1] or [2], wherein the method is reacted with an alkoxysilane compound.

[0014]

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[0015]

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[0016]

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[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. The silicon-containing compound of the present invention may be a compound represented by the formula (1), (2) or (3) (hereinafter, referred to as “first silicon-containing compound”, “second silicon-containing compound”, and “third silicon-containing compound”, respectively). Silicon-containing compound "). Hereinafter, each silicon-containing compound will be specifically described.

1. First silicon-containing compound The first silicon-containing compound is a compound represented by the formula (4) (hereinafter, may be referred to as “reactive compound (4)”).
And isophorone diisocyanate (IPDI) with a compound represented by the above formula (6) (hereinafter sometimes referred to as “reactive compound (6)”) in the presence of a catalyst.

Reactive compound (4) and reactive compound (6)
Is preferably made equimolar to IPDI.

In the production of the first silicon-containing compound, an addition reaction between IPDI and the reactive compound (6) is carried out because the reaction between the tertiary hydroxyl group of compound (4) and the isocyanate group of IPDI is prevented. After that, it is preferable to react the adduct of IPDI and the reactive compound (6) with the reactive compound (4).

In the production of the first silicon-containing compound,
The purity of the first silicon-containing compound is preferably at least 80%, more preferably at least 90%.

2. Second silicon-containing compound The second silicon-containing compound is a reactive compound (4),
2,4-tolylene diisocyanate (2,4-TDI)
Or / and 2,6-tolylene diisocyanate (2,6
-TDI) and the reactive compound (6) in the presence of a catalyst.

Reactive compound (4) and reactive compound (6)
Is preferably made equimolar to TDI.

In the production of the second silicon-containing compound, an addition reaction between TDI and the reactive compound (6) is carried out to prevent the reaction between the tertiary hydroxyl group of the compound (4) and the isocyanate group of TDI. After that, it is preferable to react the adduct of TDI and the reactive compound (6) with the reactive compound (4).

In the production of the second silicon-containing compound,
The purity of the second silicon-containing compound is preferably at least 80%, more preferably at least 90%.

3. Third silicon-containing compound The third silicon-containing compound is a compound represented by the formula (5) (hereinafter, may be referred to as “reactive compound (5)”).
And IPDI and the reactive compound (6) in the presence of a catalyst.

Reactive compound (5) and reactive compound (6)
Is preferably made equimolar to IPDI.

In the production of the third silicon-containing compound, after performing an addition reaction between IPDI and the reactive compound (5), an adduct of IPDI and the reactive compound (5) is added to the reactive compound (6). Is preferably reacted with If the order is reversed or the three components are simultaneously added and reacted, the desired silicon-containing compound may not be obtained with high purity.

In the production of the third silicon-containing compound,
The purity of the third silicon-containing compound is preferably at least 80%, more preferably at least 90%.

The reactive compound (4) used in the present invention includes, for example, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-methyl
Propan-1-one can be mentioned. Commercial products of the above compounds include Irgacure 2959, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.

The reactive compound (5) used in the present invention includes, for example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one. Examples of commercially available products of the above compounds include Darocur 1173 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.).

Examples of the reactive compound (6) used in the present invention include γ-mercaptopropyltrimethoxysilane. Examples of commercially available products of the above compounds include SH6062 (trade name, manufactured by Dow Corning Toray Silicone Co., Ltd.).

In the first to third methods for producing a silicon-containing compound, the reaction temperature is usually -20 to 100 ° C, preferably 0 to 60 ° C.

The reaction is carried out in an inert solvent, for example, a hydrocarbon solvent such as toluene, xylene, hexane or heptane, a halogenated hydrocarbon solvent such as methylene chloride, chloroform or chlorobenzene, acetone, methyl ethyl ketone or methyl isobutyl ketone. The reaction may be performed in a ketone-based solvent such as, for example, an ether-based solvent such as tetrahydrofuran, dioxane, trioxane, or diglyme, or a mixed solvent thereof. The amount of these solvents to be used is generally 1,000 ml or less, preferably 500 ml or less, more preferably 100 ml or less, per 1 mol of diisocyanate. If the amount of the solvent exceeds 1000 ml, the reaction may not proceed sufficiently.

The catalyst used in the present invention includes:
Any of a basic catalyst and an acidic catalyst may be used, and a basic catalyst and an acidic catalyst may be used in combination. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Among them, tertiary amines such as pyridine and triethylamine are preferred. Examples of the acid catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, DABCO, methyl D
Metal alkoxides such as ABCO, tributoxyaluminum, titanium tetrabutoxide, zirconium tetrabutoxide, boron trifluoride diethyl etherate,
Examples include Lewis acids such as aluminum chloride, and tin compounds such as tin 2-ethylhexanoate, octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. Among them, tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate are preferred. When a basic catalyst and an acidic catalyst are used in combination, it is preferable to use amines and a tin compound in combination. The combination is more preferred.

Among the above catalysts, a combination of a basic catalyst and an acidic catalyst is preferred, and a combination of an amine and a tin compound is more preferred. Tertiary amines such as pyridine and triethylamine and octyltin trilaurate, dibutyltin Particularly preferred is the use in combination with a tin compound such as dilaurate or octyltin diacetate.

The addition amount of these catalysts is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the diisocyanate compound. If the amount is less than 0.01 part by weight, the reaction may not proceed sufficiently,
If the amount is more than 10 parts by weight, the storage stability of the product may decrease.

The silicon-containing compound of the present invention is useful as a surface modifier for reactive particles (surface-active particles). That is, since the silicon-containing compound of the present invention has an alkoxysilane group, a radical polymerization initiating function can be imparted to the surface of the particles by reaction with various reactive particles. Useful as

[0039]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified.

Example 1 (Synthesis of First Silicon-Containing Compound) 34.3 parts of isophorone diisocyanate in dry air
Γ-mercaptopropyltrimethoxysilane was added to a solution consisting of 0.5 part of dibutyltin dilaurate.
After dripping 4 parts at 20 ° C. over 1 hour with stirring, 60 parts were added.
Stirred at C for 1 hour. After 0.1 part of triethylamine was added thereto and the mixture was stirred at 60 ° C. for 1 hour, the amount of residual isocyanate in the intermediate was analyzed, and it was 10%.
The total isocyanate amount before the reaction was 20%, and the isocyanate conversion obtained from this value was 50%. One isocyanate group in isophorone diisocyanate and γ
-It was confirmed that the reaction of the mercaptopropyltrimethoxysilane with the thiol group was almost quantitatively completed. Further, 1- [4- (2-hydroxyethoxy) phenyl]-
After adding 34.7 parts of 2-hydroxy-2-methyl-1-propan-1-one, the mixture was heated and stirred at 60 ° C. for 3 hours to obtain a first silicon-containing compound. When the amount of residual isocyanate in the product was analyzed, it was 0.1% or less,
It was confirmed that the reaction was completed almost quantitatively.

FIG. 1 shows an IR absorption curve of the obtained first silicon-containing compound.

The ¹ H-NMR spectrum data is shown below. _{^{1 H-NMR; CDC1 3 ·}} 400MHz δppm; 0.60-1.35 (m, 17H), 1.4
0-1.90 (m, 10H), 2.80-3.20
(M, 4H), 3.56 (s, 9H), 3.90-41
9 (m, 1H), 4.20-4.30 (m, 2H),
4.38-4.50 (m, 2H), 6.95 (d, 2
H), 8.06 (d, 2H)

Example 2 (Synthesis of Second Silicon-Containing Compound) 2,4-Tolylene diisocyanate in dry air
Γ-mercaptopropyltrimethoxysilane 3 in a solution consisting of 2 parts and 0.1 part of dibutyltin dilaurate
After dropping over 3.0 hours at 20 ° C. while stirring 3.0 parts,
The mixture was stirred at 30 ° C. and 60 ° C. for 1 hour each. Analysis of the amount of residual isocyanate in this intermediate revealed that it was 11.3.
%, Indicating that the reaction was almost quantitatively completed. Further, after adding 37.7 parts of 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, the mixture was heated and stirred at 60 ° C. for 3 hours, and then stirred. 2 silicon-containing compounds were obtained. Analysis of the amount of residual isocyanate in the product was 0.1% or less, indicating that the reaction was almost quantitatively completed.

FIG. 2 shows an IR absorption curve of the obtained second silicon-containing compound.

The ¹ H-NMR spectrum data is shown below. ¹ H-NMR; CDCl ₃ .400 MHz δ ppm; 0.74 (t, 2H), 1.63 (s, 6
H), 1.77 (q, 2H), 2.19 (d, 3H),
2.98 (t, 2H), 3.57 (s, 9H), 4.2
7-4.31 (m, 2H), 4.50-4.57 (m,
2H), 6.55 (s, 1H), 6.98-7.35.
(M, 4H), 7.84 (s, 1H), 8.07 (d,
2H)

Example 3 (Synthesis of third silicon-containing compound) 38.1 parts of isophorone diisocyanate in dry air
To a solution consisting of 0.1 part of dibutyltin dilaurate, 28.1 parts of 2-hydroxy-2-methyl-1-phenyl-propan-1-one was added dropwise with stirring at 20 ° C. for 1 hour. The mixture was stirred at C for 1 hour. Analysis of the amount of residual isocyanate in this intermediate was 10.9%, confirming that the reaction was almost quantitatively completed. Further, 33.6 parts of γ-mercaptopropyltrimethoxysilane, 0.1 parts of triethylamine
After the addition of 3 parts, the mixture was heated and stirred at 60 ° C. for 3 hours to obtain a third silicon-containing compound. Analysis of the amount of residual isocyanate in the product was 0.1% or less, indicating that the reaction was almost quantitatively completed.

FIG. 3 shows an IR absorption curve of the obtained third silicon-containing compound.

The ¹ H-NMR spectrum data is shown below. ¹ H-NMR; CDCl ₃ , 400 MHz δ ppm; 0.57-1.20 (m, 17H), 1.5
9-1.85 (m, 10H), 2.80-3.05
(M, 4H), 3.57 (s, 9H), 7.34-7.
58 (m, 3H), 8.00-8.11 (m, 2H)

[0049]

As described above, according to the present invention,
Novel silicon-containing compound having a radical polymerization initiating group useful as a surface modifier for reactive particles used in a resin composition capable of forming a coating film (cured film) on the surface of various substrates, and efficient production thereof A method can be provided. The resin composition using the reactive particles surface-modified with the silicon-containing compound of the present invention has excellent cured product productivity and, when formed into a cured product, has excellent high scratch resistance, high transparency, low It has curling properties and stain resistance.

[0050]

[Brief description of the drawings]

FIG. 1 is a graph showing an IR absorption curve of a first silicon-containing compound obtained in an example of the present invention.

FIG. 2 is a graph showing an IR absorption curve of a second silicon-containing compound obtained in an example of the present invention.

FIG. 3 is a graph showing an IR absorption curve of a third silicon-containing compound obtained in an example of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Keiichi Yamaguchi 2-11-24 Tsukiji, Chuo-ku, Tokyo JAE S.R. (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo JAE F-term (reference) 4H049 VN01 VP01 VQ49 VR21 VR43 VS48 VU13 VW02

Claims (3)

[Claims] 1. A silicon-containing compound represented by the following formula (1), (2) or (3). Embedded image Embedded image Embedded image 2. The silicon-containing compound according to claim 1, wherein the compound represented by the formula (2) is a 2,4-form and / or a 2,6-form. 3. A compound represented by the following formula (4) or (5):
The reaction according to claim 1 or 2, wherein isophorone diisocyanate, 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate, and an alkoxysilane compound represented by the following formula (6) are reacted. A method for producing a silicon-containing compound. Embedded image Embedded image Embedded image