JPH1112361A - Organopolysiloxane containing acrylic group and production of organopolysiloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily produce the subject compound having excellent compatibility and ultraviolet curability and giving an excellent flexible cured material by reacting an acrylic compound with a specific organopolysiloxane compound having amino groups on both terminals. SOLUTION: This organopolysiloxane containing acrylic group is expressed by the formula I (R<1> is a bivalent or trivalent 2-10C hydrocarbon group; R<2> is a bivalent 3-10C hydrocarbon group; R<3> is a univalent 1-10C hydrocarbon group; (m) is 1 or 2; (n) is 100-1,000) and is producible e.g. by the addition reaction of a compound of the formula II with a compound of the formula III. A cured coating film can be imparted with flexibility, slipperiness, water- repellency, etc., by the addition of the compound to various radiation-curable coating agents and the compound can be applied in the fields of mold-releasing coating agent, water-repellent coating agent, ink, coating material, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a novel acrylic-containing organopolysiloxane and a novel method for producing the organopolysiloxane.

More specifically, the present invention relates to a radiation-curable acrylic group-containing compound useful in the field of coating such as a release coating agent, a protective coating agent, a water-repellent coating agent, a printing ink and a paint, and a method for producing the compound. Things.

[0003]

2. Description of the Related Art As a silicone composition curable by ultraviolet rays or electron beams, an organopolysiloxane containing a (meth) acryloxy group in the molecule (Japanese Patent Publication No. 52-3190) is known. Is known,
For this, a composition further containing a sensitizer (Japanese Patent Publication No. Sho 5
3-36515) is also known. However, this kind of composition has disadvantages that the cured film becomes hard, the followability to the base material is deteriorated, and the film is easily broken because the content of the (meth) acryloxy group in the organopolysiloxane is large. .

JP-A-61-232 and JP-A-56-86922 disclose a method for producing an acrylic functional ultraviolet-curable polysiloxane by adding an epoxy group-containing organopolysiloxane and acrylic acid. However, because acrylic acid remains unreacted, moisture resistance and electrical properties are poor due to the effect of carboxyl groups remaining in the cured film, and when the amount of acrylic acid is reduced, epoxy groups remain, As a result, it has been pointed out that the weather resistance, acid resistance and the like due to the epoxy group of the surface layer after curing are lowered.

As a method for preventing acrylic acid from remaining in a radiation-curable coating agent, Japanese Patent Application Laid-Open No. 5-309
No. 664 proposes a method in which an alkoxysilyl group and a silanol compound containing a (meth) acryl group are subjected to a dealcoholization reaction in the presence of a tin catalyst to introduce a (meth) acryl group into the organopolysiloxane. However, this (meth) acryl group-containing silanol compound is difficult to synthesize and is an industrially expensive compound. Further, the remaining tin catalyst is not preferable for safety.

Further, a method for producing this kind of (meth) acryl-functional organopolysiloxane is described in US Pat.
The dehydrochlorination reaction of Cl group and hydroxy group-containing acrylate compound, the dehydrochlorination reaction of carbinol group-containing siloxane and acrylic acid chloride, and the hydrosilylation reaction of ≡Si-H group with allyl (meth) acrylate are known. However, the reaction is liable to be complicated such as by-products such as removal of hydrochloride and dehydrocondensation due to side reactions during hydrosilylation. Furthermore, since the reaction is multi-step, it cannot be said to be an industrially inexpensive and simple production method.

[0007] The present invention has been made in view of the above circumstances,
An ultraviolet-curable acrylic-containing organopolysiloxane that can form a cured product having excellent flexibility and has good compatibility with other (meth) acrylic compounds, It is an object of the present invention to provide a method for producing an acryl group-containing organopolysiloxane, which can solve the conventional method for producing a (meth) acryl-functional organopolysiloxane.

[0008]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that the acrylic compound represented by the following general formula (3) and the following general formula (4) It has been found that a novel acrylic group-containing compound represented by the following general formula (1) can be obtained by performing an addition reaction with an organopolysiloxane compound having an amino group at both terminals represented by the following formula (1).

[0009]

Embedded image (Where R ¹ is a divalent or trivalent hydrocarbon group having ² to 10 carbon atoms, R ² is a divalent hydrocarbon group having 3 to 10 carbon atoms,
R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, m represents 1 or 2, and n represents an integer of 100 to 1,000. )

In this case, an phenyl group-containing organopolysiloxane compound represented by the following general formula (5) is used as the compound of the above formula (4), whereby an acrylic group represented by the following general formula (2) is obtained. It has been found that a contained organopolysiloxane can be obtained.

[0011]

Embedded image (Wherein, R ¹ , R ² , and m have the same meaning as described above.)
Me represents a methyl group, Ph represents a phenyl group, R ⁴ represents a methyl group or a phenyl group, p represents an integer of 1 or more, q represents an integer of 10 or more, and p + q is 100 to 1000. )

That is, the present inventors have conducted various studies to develop a novel organopolysiloxane which has solved the conventional disadvantages, and as a result, have completed the acrylic group-containing organopolysiloxane represented by the general formula (1). is there. Also, as a method for easily producing an acrylic group-containing organopolysiloxane at a low cost, it has been found that an addition reaction of a diacrylate compound or a triacrylate compound of 2 mol or more and an organopolysiloxane containing both terminal amino groups is simple, The terminal amino group-containing organopolysiloxane is a material that is widely used industrially, and it has been found that the above method is a useful production method, and the present invention has been accomplished.

The organopolysiloxane of the present invention has a linear siloxane chain of 100 to 1000 and has an acrylic group at both ends, so that it is excellent in curability by radiation, and has other (meth) acrylic properties. It is compatible with the base compound and is excellent in imparting flexibility after curing. Further, by using the phenyl group-containing acryl group-containing organopolysiloxane of the formula (2), the film transparency after radiation curing is excellent.

Accordingly, the present invention provides an acryl group-containing organopolysiloxane represented by the above general formulas (1) and (2), the compounds of the above general formulas (3) and (4), and the general formula (3) And a compound of formula (1), wherein the compound of formula (1) and (2) are subjected to an addition reaction.

Hereinafter, the present invention will be described in more detail. The novel acrylic group-containing organopolysiloxane of the present invention is represented by the following general formula (1).

[0016]

Embedded image (Where R ¹ is a divalent or trivalent hydrocarbon group having 2 to 10 carbon atoms, particularly 2 to 6 carbon atoms, and R ² is 3 to 10 carbon atoms, particularly 3 carbon atoms.
A divalent hydrocarbon group of 6 to 6, R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6; m represents 1 or 2, and n represents an integer of 100 to 1000; )

[0017]

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Specific examples of R ¹ include an ethylene group, a propylene group, a butylene group, a hexamethylene group, a cyclohexylene group, a phenylene group and the following divalent or trivalent alkylene groups.

[0019]

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R ² is a straight-chain having 3 to 10 carbon atoms;
Examples thereof include a branched or cyclic alkylene group, an arylene group having 6 to 10 carbon atoms, and specifically, a propylene group, a butylene group, a hexamethylene group, a cyclohexylene group, a phenylene group, and a C3 to C4 group shown below. And 10 alkylene groups.

[0021]

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R represents 1 to 10 carbon atoms, especially 1
To 6 linear, branched or cyclic alkyl groups, 6 carbon atoms
And an aralkyl group having 7-10 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a benzyl group, a β-phenylethyl group, and an α-methyl group. A -β-phenylethyl group is exemplified, and a methyl group and a phenyl group are particularly preferred industrially. Further, in this case, in order to further enhance the solubility with other acrylic compounds, a phenyl group, β-phenylethyl group,
It is preferable to contain an aromatic hydrocarbon group such as an α-methyl-β-phenylethyl group.

The siloxane number n is 100 to 100
0 is preferable, and if it is less than 100, the flexibility of the cured film becomes insufficient, and if it exceeds 1,000, the solubility with other acrylic compounds becomes poor, which is not preferable. Particularly preferably 15
The range is from 0 to 500.

Further, an organopolysiloxane represented by the following general formula (2) is suitable for the purpose of enhancing the solubility with other acrylic compounds or the transparency of the cured film.

[0025]

Embedded image (Wherein, R ¹ , R ² , and m have the same meaning as described above.)
Me is a methyl group, Ph is a phenyl group, R ⁴ is a methyl group or a phenyl group, p is an integer of 1 or more, q is an integer of 10 or more, and p + q is 100 to 1000, particularly preferably 150 to 500. It is. )

The acrylic group-containing organopolysiloxane of the formula (1) of the present invention is represented by the following general formula (4) and one vinyl group of a diacrylate or triacrylate compound represented by the following general formula (3). It is obtained by performing an addition reaction with one of the amino groups at both ends of the organopolysiloxane containing amino groups at both ends. In this case, in particular, 2 moles per mole of the organopolysiloxane of the formula (4)
Preferably, more than one mole of a diacrylate or triacrylate compound is reacted, and the reaction conditions are room temperature to 80 ° C. for 1 to 20 hours with stirring to obtain the corresponding adduct.

[0027]

Embedded image (Wherein, R ¹ , R ² , R ³ , m, and n have the same meanings as described above.)

The organopolysiloxane containing amino groups at both ends represented by the formula (4) is mass-produced industrially and can be produced at a lower cost than conventional organopolysiloxanes containing an acrylic group. The acrylic compound of the formula (3) is required in an amount of 2 mol or more, preferably 2.5 mol or more, per 1 mol of the organopolysiloxane of the formula (4). The upper limit is preferably 4 mol. 2
If the amount is less than the mole, the amount of acrylic groups that can be cured by radiation is reduced, and the viscosity of the finished product is undesirably increased.

Further, as the organopolysiloxane containing a phenyl group and having both terminal amino groups, those represented by the following general formula (5) are preferable, and are reacted with 2 mol or more of the acrylic compound of the above general formula (3). By doing so, the corresponding adduct (organopolysiloxane of the formula (2)) is obtained.

[0030]

Embedded image (In the formula, R ² , Me, Ph, R ⁴ , m, p, and q have the same meanings as described above.)

Examples of the diacrylate or triacrylate compound represented by the general formula (3) include, but are not limited to, the following.

[0032]

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[0033]

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Specific examples of the organopolysiloxane having amino groups at both ends represented by the general formula (4) or (5) include the following. The organopolysiloxane of the present invention is obtained by reacting with an acrylate compound, but is not limited thereto. Note that M
e represents a methyl group, and Ph represents a phenyl group.

[0035]

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[0036]

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The organopolysiloxane of the present invention has excellent ultraviolet curability or electron beam curability. In particular, by adding the organopolysiloxane of the present invention to various radiation-curable coating agents, the cured film becomes flexible. , Slipperiness,
It is possible to impart water repellency and the like. It is an industrially useful compound that can impart flexibility to a radiation-curable resin that is generally hard and brittle.

Therefore, the organopolysiloxane of the present invention can be applied to the fields of release coatings, water-repellent coatings, protective coatings, various inks and paints.

The ultraviolet curable resin obtained by mixing the organopolysiloxane of the present invention is used after adding a photoinitiator. As a photoinitiator, for example, 2,2-diethoxyacetophenone, benzophenone, p-methoxybenzophenone, benzoylmethyl ether, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, acetophenone, propiophenone, xanthone, benzoyl,
Benzyl, naphthoquinone, 4-methylacetophenone,
Anthraquinone, t-butyl perbenzoate and the like can be mentioned.

When the organopolysiloxane of the present invention is added to a general radiation-curable acrylic paint as a flexibility-imparting agent, the function is exhibited at an addition amount of 1 to 20% by weight. If it is less than 1% by weight, almost no flexibility can be expected.
Exceeding the weight percentage is not preferred because it is difficult to be compatible with general acrylic paints.

The radiation used is an electron beam, α
Examples include a ray, a β ray, a γ ray, or a mercury arc, a medium pressure mercury lamp, and ultraviolet rays generated from a high pressure mercury lamp. The dose that can be cured may be about 2 to 5 Mrad with an electron beam, and a high-pressure mercury lamp (80 W / cm) of, for example, 2 kW may be used for ultraviolet rays from a distance of 8 cm for about 0.1 to 20 seconds.

[0042]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 145 g of amino silicone at both ends represented by the following average composition formula (a) and 8.5 g (4 times mol) of neopentyl glycol diacrylate were mixed and stirred at room temperature for 8 hours to obtain the following. (A) was quantitatively obtained. This product is
Viscosity (25 ° C) 1060 cp, refractive index (25 ° C) 1.4
573, showing an infrared absorption spectrum as shown in FIG.

[0044]

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Example 2 249 g of amino silicone at both ends represented by the following average composition formula (b) and 8.5 g (4 times mol) of neopentyl glycol diacrylate were mixed and stirred at room temperature for 8 hours to obtain the following. (B) was quantitatively obtained. This product is
Viscosity (25 ° C) 8750 cp, refractive index (25 ° C) 1.4
856, showing an infrared absorption spectrum as shown in FIG.

[0046]

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[0047]

The acrylic group-containing organopolysiloxane of the present invention gives a cured product having excellent flexibility, and according to the production method of the present invention, such an acrylic group-containing organopolysiloxane can be easily and inexpensively produced. I can do it.

[Brief description of the drawings]

FIG. 1 shows the product obtained in Example 1 of the present invention. Infrared absorption
It is a chart of a spectrum.

FIG. 2 shows the product obtained in Example 2 of the present invention. Infrared absorption
It is a chart of a spectrum.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Shohei Kosakai 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside Silicone Electronic Materials Technology Laboratory, Shin-Etsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. An acrylic polyorganosiloxane represented by the following general formula (1). Embedded image (Where R ¹ is a divalent or trivalent hydrocarbon group having ² to 10 carbon atoms, R ² is a divalent hydrocarbon group having 3 to 10 carbon atoms,
R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, m represents 1 or 2, and n represents an integer of 100 to 1,000. ) 2. An acryl-containing organopolysiloxane represented by the following general formula (2). Embedded image (Wherein, R ¹ , R ² , and m have the same meaning as described above.)
Me represents a methyl group, Ph represents a phenyl group, R ⁴ represents a methyl group or a phenyl group, p represents an integer of 1 or more, q represents an integer of 10 or more, and p + q is 100 to 1000. ) 3. The method for producing an acrylic group-containing organopolysiloxane according to claim 1, wherein the compound represented by the following general formula (3) and the compound represented by the following general formula (4) are subjected to an addition reaction. . Embedded image (Wherein, R ¹ , R ² , R ³ , m, and n have the same meanings as described above.) 4. The method for producing an acrylic group-containing organopolysiloxane according to claim 2, wherein the compound represented by the following general formula (3) and the compound represented by the following general formula (5) are subjected to an addition reaction. . Embedded image (Where R ¹ , R ² , Me, Ph, R ⁴ , m, p, q
Has the same meaning as described above. )