JPH0610263B2 - Polysiloxane macromonomer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel polysiloxane macromonomer.

2. Description of the Related Art Polysiloxane-based macromonomers are polysiloxanes having polymerizability. Conventionally, in the already known polysiloxane, a compound having one polymerizable unsaturated bond and one hydroxyl group or alkoxyl group at the terminal equivalent polymerizes linearly, but has a low cross-linking structure due to low reactivity of hydroxyl group and the like. It has the drawback that it is difficult to form, and it has only one hydroxyl group or alkoxyl group at both ends.
It is a compound that does not contain a collective unsaturated bond and is polymerized only by condensation, so it has the drawback of not having sufficient water resistance, chemical resistance, weather resistance, etc. Also, there is one polymerizability at each end corresponding part. A compound having an unsaturated bond has a drawback that it is difficult to handle because it easily gels during polymerization, and a graft polymer cannot be formed.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention is intended to solve the above-mentioned drawbacks of conventional polysiloxanes.

Means for Solving the Problems The present inventor uses a specific raw material to produce polysiloxane 1
Polymerization and condensation in a novel polysiloxane macromonomer obtained by having an average of one polymerizable unsaturated bond per molecule and at least two or more hydroxyl groups and / or alkoxyl groups at the terminal equivalent It was found that the above can be carried out separately, and that they can be crosslinked by condensation without gelation during polymerization, and the above-mentioned object can be sufficiently achieved, and based on this, the present invention was completed.

That is, the present invention has the general formula (In the formula, R ₁ represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and R ₂ , R ₃ and R ₄ have 1 to 4 carbon atoms.
Represents an aliphatic hydrocarbon group or a hydrogen atom. ) 70 to 99.999 mol% of the compound (A) represented by (In the formula, R ₅ is a hydrogen atom or a methyl group, and R ₆ , R
₇ and R ₈ represent a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. However,
Except the case where all of R ₆ , R ₇ and R ₈ are an aliphatic hydrocarbon group having 1 to 8 carbon atoms. n shows the integer of 1-6. The compound (B) represented by the formula (1) is reacted with 30 to 0.001 mol% of the compound (B), and an average of one polymerizable unsaturated bond per molecule and at least two or more hydroxyl groups and (or ) An alkoxy group, wherein the group corresponding to the terminal is represented by the general formula (In the formula, R ₁ , R ₂ and R ₃ have the same meanings as described above.) And / or the general formula (Wherein R ₁ , R ₂ and R ₃ have the same meanings as described above), and the repeating unit is represented by the general formula (In the formula, R ₁ and R ₂ have the same meanings as described above.) And / or a general formula (In the formula, R ₁ has the same meaning as described above.), And relates to a polysiloxane macromonomer having a number average molecular weight of 400 to 100,000.

In the present specification, the “portion corresponding to the non-end” means one or two or more Si located at the end of the polysiloxane macromonomer.

In the present specification, examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include linear or branched ones such as methyl group, ethyl group, propyl group and butyl group,
In addition to the above groups, examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include straight-chain or branched ones such as pentyl group, hexyl group, heptyl group and octyl group. Examples of the alkoxyl group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group,
Examples thereof include linear or branched butoxy groups.

In the polysiloxane-based macromonomer of the present invention, the main skeleton is composed of siloxane bonds, and Si of the main skeleton has an aliphatic hydrocarbon group, a phenyl group, a hydroxyl group, an alkoxyl group, a polymerizable unsaturated bond, etc. directly or indirectly. And is obtained by reacting the compound (A) with the compound (B).

First, the compound (A) is a compound represented by the general formula (I), and based on the general formula, a methyl group and a phenyl group are particularly preferable as R ₁ . R ₂ , R ₃ and R ₄ may all be the same or partly or wholly different.

As R ₂ , R ₃ and R ₄ , a methyl group, an ethyl group,
Propyl group, butyl group and hydroxyl group are preferred. Specific preferred examples of the compound (A) include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxylane, methyltributoxysilane, phenyltrisilanol and methyltrisilanol. Of these, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltrisilanol and the like are particularly preferably used.

Next, the compound (B) is a compound represented by the above general formula (II), and based on the general formula, R ₆ , R ₇ and R ₈ are all the same or different in part or all. May be. However, all must not be aliphatic hydrocarbon groups having 1 to 8 carbon atoms. R ₆ , R ₇ and R ₈ are particularly preferably a methoxy group, an ethoxy group or a hydroxyl group, and n is particularly preferably in the range of 2-4. Specific preferred examples of the compound (B) include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane and γ.
-Methacryloxybutyltriethoxysilane, γ-acryloxypropyltrisilanol and the like can be mentioned. Of these, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrisilanol and the like are particularly preferable.

The siloxane-based macromonomer of the present invention is obtained by mixing the compound (A) and the compound (B) and reacting them. The mixing ratio of both compounds is 70 to 99.999 based on the total amount of both compounds.
Mol%, preferably 90 to 99.9 mol%, more preferably 95 to 99 mol%, compound (B) 30 to 0.0.
It is in the range of 01 mol%, preferably 10 to 0.1 mol%, and more preferably 5 to 1 mol%. Compound (A) is 7
If it is less than 0 mol%, it tends to be difficult to polymerize linearly and gelation tends to occur, while 99.999 mol%
When it is used in a larger amount than that, it is not preferable because water resistance, chemical resistance, weather resistance and the like are deteriorated due to polymerization mainly due to condensation.

The reaction between the compound (A) and the compound (B) is carried out by dehydration condensation of the hydroxyl groups contained in both compounds and the hydroxyl groups generated by hydrolysis of the alkoxyl group, and the target macromonomer is produced. At this time, not only dehydration condensation but also partial dealcoholization condensation occurs depending on the conditions.

When both the compound (A) and the compound (B) have a hydroxyl group bonded to Si, they can react without a solvent, but under heating and stirring in an organic solvent that can dissolve both compounds and is inert to both compounds. It is preferable to carry out dehydration condensation reaction. As the organic solvent, various hydrocarbon-based, ester-based, ketone-based, and alcohol-based solvents can be used.

When the compound (A) and / or the compound (B) has an alkoxyl group bonded to Si, it is preferably hydrolyzed prior to the condensation, and usually hydrolyzed by heating and stirring in the presence of water and a catalyst. , Can be condensed. The amount of water used in this case is not particularly limited, but is preferably 0.1 mol or more per mol of the alkoxyl group. If the amount is less than 0.1 mol, the reaction of both compounds may decrease. The most preferable method is to use water as a solvent in a large excess. Further, as the catalyst in this case, an acid catalyst or an alkali catalyst can be used, and specifically, as the acid catalyst, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid or the like can be used, Sodium hydroxide as an alkaline catalyst,
Triethylamine, ammonia, etc. can be used. The amount of the catalyst added is about 0.0001 to 5% by weight, preferably 0.0, relative to the total amount of the compound (A) and the compound (B).
A range of 1 to 0.1% by weight is suitable.

A suitable reaction temperature for the above reaction is usually about 20 to 180 ° C, preferably 50 to 120 ° C. The reaction time is usually about 1 to 40 hours.

In this reaction system, a water-soluble organic solvent, a polymerization inhibitor, etc. may be added. The water-soluble organic solvent is effective for homogenizing the reaction system when a sparingly water-soluble alcohol is produced by condensation, and for example, alcohol-based, ester-based, ether-based, and ketone-based ones can be preferably used. The polymerization inhibitor is effective for preventing the unsaturated bond contained in the compound (B) from polymerizing during the reaction with the compound (A), and specifically, hydroquinone, hydroquinone monomethyl ether, etc. can be used. .

In the production of the polysiloxane-based macromonomer of the present invention, tetraalkoxysilane or dialkylalkoxysilane may be used in combination in the reaction system of the compound (A) and the compound (B). It can be used in combination with 20 mol% or less of the compound.

The main skeleton of the polysiloxane macromonomer of the present invention obtained by the reaction of the compound (A) and the compound (B) is
The structure of the main skeleton is constituted by a siloxane bond, and the structure of the main chain is mainly a long chain (linea) represented by the general formula (V).
Examples thereof include r), ladders represented by the general formula (VI), and mixed systems thereof. Further, the structure of the terminal group of the macromonomer has a structure represented by the general formula (III) or (I
Examples include those represented by V). These structures can be arbitrarily selected according to the mixing ratio of the compound (A) and the compound (B), the blending amount of water and the acid catalyst, and the like. Then, to the Si of the siloxane bond, any one of R ₁ , R _{2 to} R _{4 in} the general formulas (I) and (II), Any of R _{6 to} R _{8 and} the like are bonded.

Particularly, regarding the polysiloxane-based macromonomer of the present invention,
Having an average of one polymerizable unsaturated bond per molecule,
And the hydroxyl group and / or carbon number is 1 in the uncorresponding part.
At least two functional groups (such as R _{2 to} R ₄ and R _{6 to} R ₈ ) such as alkoxyl groups of ˜4 are bonded. It is naturally possible that the functional group is bonded to a portion other than the uncorresponding portion of the polysiloxane macromonomer.

The number average molecular weight of the polysiloxane macromonomer of the present invention is usually in the range of about 400 to 100,000, and the viscosity of a 50 wt% isobutyl acetate solution at 20 ° C. is usually in the range of about 0.5 to 500 centipoise. .

The polysiloxane-based macromonomer of the present invention has an average of one polymerizable unsaturated bond per molecule and at least two or more hydroxyl groups and / or alkoxyl groups at the end-corresponding part, so that it can be directly polymerized. It can be polymerized in a chain form, or can be polymerized or have a crosslinked structure by condensation of a hydroxyl group and / or an alkoxyl group and the like. Further, a crosslinked structure can be easily formed by performing both polymerization and condensation.

The polysiloxane-based macromonomer of the present invention can be polymerized and condensed separately, does not gel during polymerization, can form a graft polymer, and can be easily crosslinked by condensation. Polymers or (and) condensates that have suitable properties and are obtained by using them have water resistance, chemical resistance, weather resistance, heat resistance, light resistance, abrasion resistance, water repellency, and stain resistance. And so on. In particular, the polymerization or / and condensate obtained by using the ladder-shaped macromonomer of the present invention has remarkably good water resistance, heat resistance, light resistance and the like.

Therefore, the macromonomer of the present invention itself and the polymerized and / or condensate obtained by using the macromonomer can be used in a wide range of coating resin components, printing inks, laminating agents, molded products, adhesives, surface treatment agents, impregnation strengthening agents, etc. It can be used for various purposes.

Next, the use of the macromonomer of the present invention will be described in more detail.

The macromonomer of the present invention can be polymerized linearly or three-dimensionally by irradiating the macromonomer alone or in a mixture with another vinyl monomer with an electron beam or an ultraviolet ray. That is,
The macromonomer alone or in a mixed system with a monofunctional monomer having one polymerizable unsaturated bond polymerizes linearly, and in a mixed system with a polyfunctional monomer having two or more polymerizable unsaturated bonds, it is tertiary. Originally crosslinks and hardens. As the monofunctional monomer, an esterified product of acrylic acid or methacrylic acid and a monohydric alcohol (having 1 to 22 carbon atoms), hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate,
Methylol (meth) acrylamide, styrene, acrylonitrile, acrylic acid, methacrylic acid, vinyltoluene and the like can be mentioned. As the polyfunctional vinyl monomer, neopentyl glycol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate
Acrylate, dipentaerythritol hexa (meth)
Examples thereof include acrylate, butanediol di (meth) acrylate, and diethylene glycol di (meth) acrylate.

The mixing ratio of the macromonomer of the present invention and another vinyl monomer can be arbitrarily interpreted according to the purpose, but the macromonomer is contained in an amount of 150 to 100% by weight, preferably 50 to 100% by weight, based on the total amount of both components. Other vinyl monomers are suitable in an amount of 90 to 0% by weight, preferably 50 to 0% by weight.

When the mixture of the macromonomer of the present invention and another vinyl monomer is used as a paint component, a color pigment, an extender pigment, a rust preventive pigment, a metallic pigment, water, an organic solvent and the like can be further added.

Electron beam sources include Kotskcroft type, Kotskcroft Walwarton type, Van de Graaf type, resonant transformer type, transformer type, insulated core transformer type, dynamitron type,
There are linear filament type and high frequency type. The electron beam irradiation conditions are not particularly limited, but a dose of 1 to 20 megarads is suitable.

Further, examples of the ultraviolet radiation source include a mercury lamp, a xenon lamp, a carbon arc, a metal hydrate lamp, and sunlight. Irradiation conditions of ultraviolet rays are not particularly limited, but it is preferable to perform irradiation for several seconds or more in air or in an inert gas atmosphere. In particular, when irradiating in air, it is preferable to use a high pressure mercury lamp.

When curing by ultraviolet irradiation, it is preferable to add a photopolymerization initiator in advance. As the photopolymerization initiator, a usual photopolymerization initiator that is excited by irradiation of ultraviolet rays to generate a radical is used, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, Examples thereof include benzoin n-butyl ether, benzophenone, P-methylbenzophenone, Michler's ketone, acetophenone, 2-chlorothioxanthone, anthraquinone, 2-methylanthraquinone, phenyldisulfide, and 2-nitrofluorene. These photopolymerization initiators may be used either individually or in combination of two or more. The blending amount thereof is preferably 0.1 to 10% by weight of the mixture with the macromonomer or other vinyl monomer.

Further, a photosensitization accelerator may be used in combination with the photopolymerization initiator in order to accelerate the photopolymerization reaction by the photopolymerization initiator. Examples of the photosensitizer include tertiary amines such as triethylamine, triethanolamine and 2-dimethylaminoethanol, alkylphosphine compounds such as triphenylphosphine and thioether compounds such as β-thiodiglycol. can give.

Further, this macromonomer can be condensed alone or by mixing with a siloxane-based monomer, oligomer or polymer having another hydroxyl group and / or an alkoxyl group, and heating them or compounding a catalyst, A polymer or crosslinked product having a polymerizable unsaturated group is obtained. This is because, for example, the condensation cures the undercoat film by a reaction, then the polymerizable coating composition is applied, and when polymerized, the polymerizable unsaturated bonds remaining in the undercoat film are also polymerized. It can be used for improving the interlayer adhesion between films. Examples of the siloxane-based monomer, oligomer or polymer include tetraethoxysilane, methyltriethoxysilane, terminal hydroxyl group dimethyl (diphenyl) polysiloxane polymer, phenyltrisilanol, diphenyldisilanol, etc. Examples thereof include acids such as hydrochloric acid, sulfuric acid and acetic acid, bases such as triethylamine, methyldiethanolamine and triethanol, tin compounds such as dibutyltin diacetate and chelate compounds such as trisacetylacetonatoaluminum.

The above-mentioned polymerization and condensation can be carried out in the same system.

Examples Examples and reference examples of the present invention will be shown below.

Example 1 Methyltrimethoxysilane 2720 g (20 mol) γ-methacryloxypropiyl 256 g Lutrimethoxysilane (1 mol) Deionized water 1134 g 6% by weight hydrochloric acid 2 g Hydroquinone 1 g These mixtures were reacted at 80 ° C. for 5 hours. The number average molecular weight of the obtained polysiloxane macromonomer is 20.
00, one vinyl group (polymerizable unsaturated bond) per molecule on average, and four hydroxyl groups at the terminal equivalent. The viscosity of a 50 wt% isobutyl acetate solution of this macromonomer at 20 was 5 centipoise.

Example 2 Phenyltrisilanol 7800 g (50 mol) γ-acryloxypropy 200 g Lutrisilanol (1 mol) Toluene 4500 g These mixtures were reacted at 117 ° C. for 3 hours for dehydration. The number average molecular weight of the obtained polysiloxane-based macromonomer was 7,000, and it had one vinyl group per molecule on average and 5 to 10 hydroxyl groups in the terminal-corresponding portion. 2% of 50 wt% isobutyl acetate solution of this macromonomer
The viscosity at 0 ° C. was 150 centipoise.

Example 3 48 mol of phenyltrimethoxysilane and 2 mol of γ-methacryloxyethyltriethoxysilane were reacted in the same manner as in Example 1. The number average molecular weight of the obtained polysiloxane-based macromonomer was about 5000, and on average, one molecule had one vinyl group and 5 to 10 methoxy groups in the terminal equivalent portion. 50 of this macromonomer
The viscosity of the wt% isobutyl acetate solution at 20 ° C. was 70 centipoise.

Example 4 29.1 mol of methyltrimethoxysilane and 0.9 mol of γ-acryloxyethyltriethoxysilane were used in Example 1.
The reaction was performed in the same manner as in. The number average molecular weight of the obtained polysiloxane-based macromonomer was about 15,000, and each molecule had one vinyl group and 5 to 10 methoxy groups at the terminal equivalent on average. The viscosity of a 50 wt% isobutyl acetate solution of this macromonomer at 20 ° C. is 22.
It was 0 centipoise.

Reference Example 1 The macromonomer of Example 1 (500 g), trimethylolpropane triacrylate (500 g) and benzoin ethyl ether (20 g) were mixed and applied to an iron plate by spraying to a film thickness of 50 μ, and then set at 25 ° C. for 30 minutes, and then 2 KW.
It was cured by irradiation with a high pressure mercury lamp for 30 seconds. Further 150
When baked at 30 ° C. for 30 minutes, a hard coating film having excellent water repellency was obtained.

Reference Example 2 To 100 g of the macromonomer synthesized in Example 2, 1,6
-Hexadiacrylate (200 g) and n-butyl methacrylate (30 g) were spray-painted on a mild steel plate, left at 20 ° C for 30 minutes, and then irradiated with an electron beam at 6 Mrad to form a coating film having a pencil hardness of H. Further, when baked at 180 ° C. for 30 minutes, the hardness of the cured film was 6H and the abrasion resistance was excellent.

Reference Example 3 An iron plate was coated with the composition of Reference Example 1 and heated at 160 ° C. for 30 minutes.
Bake for a minute, and then apply photo-curable polymerizable unsaturated paint,
Then, irradiation with a 2 kW high-pressure mercury lamp was performed for 60 seconds to form a cured multilayer coating film having excellent interlayer adhesion.

Reference Example 4 The composition of Reference Example 2 was coated on a mild steel plate and the temperature was adjusted to 3 at 180 ° C.
After baking for 0 minutes, coating with a polymerizable unsaturated resin coating, and then irradiating with an electron beam at 6 Mrad, a cured multilayer coating film excellent in interlayer adhesion could be formed.

Claims (1)

[Claims] 1. A general formula (In the formula, R ₁ represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and R ₂ , R ₃ and R ₄ have 1 to 4 carbon atoms.
Represents an aliphatic hydrocarbon group or a hydrogen atom. ) 70 to 99.999 mol% of the compound (A) represented by (In the formula, R ₅ is a hydrogen atom or a methyl group, and R ₆ , R
₇ and R ₈ represent a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. However,
Except the case where all of R ₆ , R ₇ and R ₈ are an aliphatic hydrocarbon group having 1 to 8 carbon atoms. n shows the integer of 1-6. ) The compound (B) represented by the formula (1) is reacted with 30 to 0.001 mol% of the compound (B), and an average of one polymerizable unsaturated bond per molecule and at least two or more hydroxyl groups and (or ) An alkoxy group, wherein the group corresponding to the terminal is represented by the general formula (In the formula, R ₁ , R ₂ and R ₃ have the same meanings as described above.) And / or the general formula (Wherein R ₁ , R ₂ and R ₃ have the same meanings as described above), and the repeating unit is represented by the general formula (In the formula, R ₁ and R ₂ have the same meanings as described above.) And / or a general formula (In the formula, R ₁ has the same meaning as described above.) A polysiloxane macromonomer having a number average molecular weight of 400 to 100,000.