JPH01230668A - Radiation-curable organopolysiloxane composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in cohesiveness and adhesiveness by mixing an organopolysiloxane with an organosilyl peroxide compound. CONSTITUTION:This radiation-curable organopolysiloxane composition comprises an organopolysiloxane and an organosilyl peroxide. Said organopolysiloxane may be a linear, branched or cyclic one among which the and linear one is preferable. Examples thereof particularly desirably used include a mixture of a vinyloxyethylpropyl organopolysiloxane with a mercaptopropyl organopolysiloxane and (meth)acryloxypropyl organopolysiloxane. Examples of the organosilyl peroxide compounds include organosilyl hydroperoxide, bis(organosilyl) peroxide and alkylperoxyorganosilane.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a radiation-curable organopolysiloxane composition, and particularly to a radiation-curable organopolysiloxane composition that exhibits good adhesion and adhesion to a substrate. relating to things.

(Prior Art) Organopolysiloxane compositions are used in a wide range of applications, such as coating materials such as optical fiber coating materials, release coating materials, printed circuit board coating materials, and botting gels. Organopolysiloxane compositions used in these applications are required to be cured and sufficiently adhere or adhere to substrates such as quartz glass, paper, plastics, metal plates, and the like.

Conventionally, organopolysiloxane compositions have been cured by room temperature curing reactions such as condensation reactions using platinum catalysts, addition reactions,
This is done using a heat curing reaction using an organic peroxide.

In recent years, in order to further increase the curing rate of organopolysiloxane compositions, many methods of curing organopolysiloxane compositions using radiation such as ultraviolet rays and electron beams have been proposed, and some of them are being put into practical use.

[Problems to be Solved by the Invention] However, when conventional organopolysiloxane compositions were applied to radiation curing reactions, sufficient properties in terms of adhesion and adhesion to substrates could not be obtained.

Therefore, an object of the present invention is to provide a radiation-curable organopolysiloxane &[[171] which has excellent adhesiveness and adhesion.

[Means for Solving the Problems] To solve the above problems, the present invention provides a radiation-curable organopolysiloxane composition containing (^) organopolysiloxane and (B) an organosilyl peroxide compound. It is something to do.

The organopolysiloxane which is the component (A) of the composition of the present invention may be one or more selected from compounds represented by the following formula (I): R'J"bSiO, (1) It is a mixture of compounds.

In the formula (1), R1 is a hydrogen atom; an aliphatic unsaturated group such as a vinyl group, (meth)acryloxypropyl group, allyl group, 1-butenyl group, -hexenyl group, R'SR'
-(Here, R3 is a hydrogen atom or a substituted or unsubstituted organic group, for example, C1,.CHO(CI+□+).

C1,・Cll C1(J(Ct(a group represented by z+z, preferably a hydrogen atom. R4 is a divalent substituted or unsubstituted hydrocarbon group, such as trimethylene group, ethylene group, methylene and tetramethylene group, preferably trimethylene group), and preferably a hydrogen atom, vinyl group, mercaptopropyl group, (meth)acryloxypropyl group, etc. R2 is 1 a valent substituted or unsubstituted hydrocarbon group,
For example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, aryl groups such as feni/14, tolyl group,
Cycloalkyl groups such as cyclohexyl groups, or groups in which some or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc., such as 3,
3.3-Trifluoropropyl group, cyanmethyl group, etc. are mentioned. a is 0≦a≦1, preferably 0.010
≦a≦0.20, and b is 0≦b≦3, preferably 1
．． 8≦b≦2.2, and 0≦a+b≦3. If a is too large, the crosslinking density will be too high and the obtained cured product will be brittle and have insufficient mechanical strength, while if a is too small, curing will not be sufficient.

The organopolysiloxane of component (8) of the present invention may be linear, branched, or cyclic, and preferably linear.

Particularly preferred as component (A) are a mixture of an organopolysiloxane containing a vinyloxyethylthiopropyl group and an organopolysiloxane containing a mercaptopropyl group, a mixture of an organopolysiloxane containing a mercaptopropyl group and an organopolysiloxane containing a vinyl group, It is a mixture of a vinyl group-containing organopolysiloxane and a hydrogen atom-containing organopolysiloxane, or a (meth)acryloxypropyl group-containing organopolysiloxane. (A)
When a mixture of two types of compounds is used as a component, it is desirable that the number of functional groups contained in each of the two types of compounds in the mixture is equal to each other, but one of the functional groups is preferably 0.5 to 0.5 to It may be twice the molar amount. however,
If a large amount of one of the functional groups remains after curing, various physical properties such as heat resistance will deteriorate. In addition, when a mixture of a vinyl group-containing organopolysiloxane and a hydrogen atom-containing organopolysiloxane is used as component (A), a sensitizer such as acetophenone, benzophenone, 4-methoxybenzophenone, benzoin isobutyl ether, etc. is used for the curing reaction. It is preferable to add it.

The organosilyl peroxide compound which is component (B) of the composition of the present invention contains a unit represented by the following formula (): % formula %) in one molecule. In the above formula (II),
R4 is an atomic group represented by a hydrogen atom; -3i, -C, t-butyl group, α, α-dimethylbenzyl group, etc., preferably a hydrogen atom; -5i EEE -C
It is an L-butyl group.

Examples of the organosilyl peroxide compound having the above unit in the molecule include organosilyl hydroperoxide, bis(organosilyl) peroxide, and alkylperoxyorganosilane.

Specific examples of the organosilyl hydroperoxide include triphenylsilyl hydroperoxide, methyl-diphenylsilyl hydroperoxide, tribenzylsilyl hydroperoxide, tri-n-hexylsilyl hydroperoxide, vinyl-phenyl-methylsilyl Specific examples of bis(organosilyl)peroxides include bis(triphenylsilyl)peroxide, bis(trimethylsilyl)peroxide, bis(n-butyl-dimethylsilyl)peroxide; Specific examples of oxyorganosilanes include trimethyl(t-butylperoxy)silane, tri-n-butyl(t-butylperoxy)silane, aryl-dimethyl(t-butylperoxy)silane, vinyl-diphenyl(α, α-dimethylbenzylperoxy)silane, vinyl-tris(
t-7' tylperoxy) silane, vinyl-methylbis(t-butylperoxy)silane, vinylphenylbis(t-butylperoxy)silane, or Me3SiOO
It is expressed by a formula such as Siph3 or ViMezSiooSiphs.

The organosilyl peroxide compound as the component (B) can be produced, for example, by the following method.

Organosilyl hydroperoxide can be easily produced using the corresponding organochlorosilane and hydrogen peroxide as shown in the reaction formula below.

1? lSiCl + HzOz→ R,5iOOH+I
ICIHCf+NH,→NI1. H(/! Bis(organosilyl)peroxide can be produced using organosilyl hydroperoxide and organochlorosilane as shown in the following formula.

MeJ+Ph1Si00H-+pH:+5iOO-+M
eJH'PhxSr00- +Ph-rs:QCjl!
−+ (PhtSt00SiP113CE −)−−
→Ph, 5i00SiPht+Cj! - or PhzSioo-+Pt++5iNHz→[ph3si
ooffsph3NnZ-]PhzSiOOH →PhxSiOOSiPt++ + N113 + P
h5Si00-alkylperoxyorganosilane is
-R4-n5iXn + mR' 00B -4 in Jl
Ra-r+5i(OOR'). +m1lX [Here,
n = 1 to 4, X: hydrocarbon group such as C1, Br, P, alkyl group, allyl group] In the composition of the present invention, the amount of the component (B) blended is usually that of the component (A). The amount is 0.1 parts by weight or more, preferably 0.5 to 2 parts by weight, per 100 parts by weight. If the amount of component CB) is too small, it will not be possible to develop sufficient adhesive properties, and if it is too large, the physical properties of the cured organopolysiloxane will deteriorate.

Stronger adhesion may be imparted to the composition of the present invention, if necessary, by adding conventionally known adhesion aids such as hydrogen silane, siloxane, and various carbon-substituted silanes. can. Silica may also be added as a reinforcing filler to the extent that the transparency of the composition of the present invention is not significantly impaired. This silica is preferably fumed silica whose silanol surface has been treated with an organosilane, particularly trimethylsilane or hexamethyldisilane. , and other substances commonly added to improve properties.

When the composition of the present invention is applied to a substrate and cured, its viscosity can be appropriately determined depending on the amount of application, the application method, the substrate to be applied, and the like. From the viewpoint of workability during application and control of application amount, the viscosity at 25°C is approximately 10.00.
The viscosity is preferably 0 cP or less, but if the viscosity is higher than this, it may be diluted with a solvent to lower the viscosity before coating.

If the adhesion between the base material and the composition of the present invention is not sufficient when the composition of the present invention is applied to the base material, there is a method of applying a primer or the like to the surface of the base material for adhesion. The adhesion between the base material and the composition of the present invention can be improved by known methods such as surface roughening and plasma treatment.

The composition of the present invention has improved adhesion to various substrates compared to conventional ones, so it can be used as a release agent for release papers and plastic films; It can be widely applied as a coating material, etc.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that "1 part" and "%" on each side below indicate parts by weight and % by weight, respectively.

Examples 1 to 3, Comparative Example 1 Following formula (d): (CHz) 3siO((CHt) zsio ) 2
:13-((CH3)(SHC)lzcHzcHz)S
iO) +5Si(CHz)i(d) Mercapto group-containing organopolysiloxane 4
0 parts and the following formula (e): C1l□=CH-MezSiO(MezSiO) 46
9 (Me-Visit) ssiMezclI=c
1.0 part of benzoin isobutyl ether was added to 60 parts of methylvinylorganopolysiloxane represented by IIz(e) and mixed uniformly.

On each side, 100 parts by weight of the mixture obtained above,
A composition was prepared by adding and mixing 1% of the organosilyl peroxide compound shown in Table 1. The obtained composition was poured between two stacked quartz plates with two gaps between them. The composition filled between the quartz plates was exposed to 10 c of ultraviolet light (hereinafter abbreviated as UV) using an 80 W/cm high-pressure mercury lamp.
A sample was prepared by curing the sample by irradiating it for 2.5 seconds from a height of m. The shear adhesive strength and cohesive failure rate of the obtained sample were measured by the following methods. The results are shown in Table 1.

Tensile speed is 50 mm using a base search castrograph (manufactured by Toyo Seiki).
/+++in.

It was calculated from the following formula based on the fracture state of the sample after the completion of the shear adhesive strength test. (Here, cohesive failure area, soil interface peeling area) = coating area of the composition) Table 1 ■ Note *1 Nitrimethyl (t-butylperoxy) silane *2: Vinyltris (t-butylperoxy) silane * 3: Vinyl phenylbis (t-butylperoxy)
Silane Examples 4 to 6 α,ω-Divinylpolydimethylsiloxane with a viscosity of 1 and 0OOcP was subjected to an addition reaction with methyldichlorosilane using a platinum catalyst to produce dimethylpolysiloxane whose both ends were blocked with methyldichlorosilane. Obtained. To this, triethylamine (EtJ) and 3.5-bis-t-butyl-
After adding 4-hydroxytoluene, 6% by weight of α-acryloxymethyldimethylsilanol was added dropwise to 60% by weight.
After reacting for 2 hours at °C, the product was filtered. The resulting oil was stripped under conditions of 100'C/2 mm Hg.

The obtained oil has a viscosity of 1230 cP and a refractive index of 1.40.
69, and was an organopolysiloxane having a structure represented by the following formula (H):

On each side, vinyltris(t-butylperoxy)silane (abbreviated as VBS) was added to the above organopolysiloxane according to the formulation shown in Table 2 to obtain a composition.

Table 2 The above compositions on each side were coated on a commercially available glass epoxy laminate to a thickness of 1. OJ/CD UV 2
A bonded sample was prepared by irradiating the sample for seconds and curing it.

After this adhesive sample was left in an environment of 85° C. and 85% relative humidity for 100 hours, the adhesiveness was measured, and the samples of Examples 5 and 6 were still sufficiently adhered. In the sample of Example 4, no peeling was observed, but bubbles (voids) were generated in a part of the interface.

Furthermore, when the rubber physical properties of the cured sample of Example 5 were measured, the hardness (JIS) was 10, and the tensile strength was 3.2.
kg/cnl and elongation of 150%, and the volume resistivity was 10'3 Ω·1.

Examples 7 to 8, Comparative Example 2 Dimethylpolysiloxane with both ends capped with trivinylsilyl groups (viscosity 1500 cP) 1 to 100 parts:S
6 parts of methylhydrodiene polysiloxane with a viscosity of 20 cP and a content of iH groups of 556 mol/100 g and 0.3 parts of 3.5-dimethyl-1-hexyn-3-ol.
200 ppm of soluble platinum was added in terms of platinum based on 1 part and 1 part of siloxane, and 0.3 part of 4-methoxybenzophenone was further added and mixed uniformly.

On each side, the organosilyl peroxide compounds shown in Table 3 were added to the mixture obtained above to prepare a composition. This composition was applied to a polyester film at a rate of 1 g/
rrf and a 2KW high pressure mercury lamp (80W/C11
) Using two UV lamps, apply UV light for 2 seconds from a distance of 10 cm.
A cured sample was obtained by irradiating and curing.

The peel force of the obtained cured sample was measured and a shedding test was performed according to the following method. The results are shown in Table 3.

■A 180@beer test was conducted using Olipine (manufactured by Toyo Ink ■) as an adhesive.

Dish 1 The surface of the cured limp sample was rubbed 10 times with a fingertip to determine whether or not it fell off.

Table 3 Water injection 4: Same as that used in Example 2 *5: Example 3
[Effects of the Invention] The radiation-curable organopolysiloxane composition of the present invention is cured by radiation, and the resulting cured product has excellent adhesion and adhesion to the substrate. .

Agent Patent Attorney Shushi Iwamiya

Claims (8)

[Claims] (1) (A) Organopolysiloxane and (B) Organosilyl peroxide compound A radiation-curable organopolysiloxane composition comprising: (2) The radiation-curable organopolysiloxane composition according to claim 1, wherein the organopolysiloxane is a mixture of a mercaptopropyl group-containing organopolysiloxane and a vinyl group-containing organopolysiloxane. thing. (3) The radiation-curable organopolysiloxane composition according to claim 1, wherein the organopolysiloxane is a (meth)acryloxypropyl group-containing organopolysiloxane. (4) The radiation-curable organopolysiloxane composition according to claim 1, wherein the organopolysiloxane is an organopolysiloxane containing a vinyl group-containing organopolysiloxane and a hydrogen atom bonded to a silicon atom. A composition that is a mixture of (5) The radiation-curable organopolysiloxane composition according to claim 1, wherein the organopolysiloxane is a vinyloxyethyl group-containing organopolysiloxane. (6) The radiation-curable organopolysiloxane composition according to claim 1, wherein the organosilyl peroxide compound is vinyl-tris(t-butylperoxy)silane. (7) The radiation-curable organopolysiloxane composition according to claim 1, wherein the organosilyl peroxide compound is methyl-phenyl-di-vinylsilyl hydroperoxide. (8) The radiation-curable organopolysiloxane composition according to claim 1, wherein the sulganosilyl peroxide compound is vinyl-phenyl(t-butylperoxy)silane.