JPS60104158A - Curable organopolysiloxane composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable organopolysiloxane composition, particularly to a curable organopolysiloxane composition that provides a rubber elastic coating with no surface tack upon short-term irradiation with ultraviolet rays, radiation, or electron beams. It is something.

Regarding silicone compositions capable of forming rubber elastic films, organopolysiloxanes containing hydroxyl groups at both ends are polyfunctional compounds capable of water decomposition. ,! 1
ljjF')jj"'l': (in' [no change to ") runner or logisan and a carrier such as heavy metal carboxylic acid, +i is added, and these are condensed.
Platinum thread 11pjHIJ with vinyl methyl hollysiloxane and puruganohydrodienesiloxane! Existence of /-'1
The addition reaction described below is considered to be one-dimensional, or the one caused by this condensation reaction takes a long time to cure, and the disadvantage is that the condensate shrinks due to the 1' t (t) of the condensate during curing. 11
・Cure II+ is weak at low temperatures such as -
A constant disadvantage of ψ-formable siloxanes is that the pot life of a mixture of these siloxanes is within a few minutes.
・That's one.

Therefore, Cure? A group 1 compound consisting of an organopolysiloxane containing mercaft and an organopolysiloxane containing tonyl chloride, which can be vortex-cured by ultraviolet rays of 1/1, has also been proposed. Cow jp public l'
1' (Publication No. 54-6512, Cow, ``1 Publication 1987-:
(Refer to Publication No. 4318 +t<+ > is this angle, i (acid is from now on)
,: White material has a limited surface tackiness, rubber strength IW, and does not have desirable physical properties as a rubber elastic body. Therefore, it is an excellent rubber bullet f'l, leather IIφ However, it has the drawback of being difficult to give a polyfunctional vinyl base, and the method of curing a composition consisting of a polyfunctional vinyl base organopolysiloxane and 4jJ peroxide by ultraviolet irradiation (1976-12'512) ;Refer to the publication number)
has the disadvantage of having a high 4th history IW.

The A5'' invention relates to a curable organopolysiloxane composition that solves these disadvantages, in which R1, R2, and R3 are the same or do not contain unsaturated bonds. Organopolysiloxane (100 parts, 111 parts, monovalent hydrocarbon, a is 2 or 3, n is a positive number) whose molecular chain end is a polyvinyl group (kJC) -B) -1
Throw 2 R5 to \C2r<' to j' Lukirenno, (, J (51 engineering 1
It is indicated by (j, L rule no (-1) +: K (1 - '2 for 1 year old). Alkyrno] (1 gui 1 meruganobori 1) [J Kiza 701-50 middle: I; τ'
Jf-e) I So 11 Winter 1110-10 71. Qi-
The fact that it consists of is ノ1 and 1°1 (also σ).

Ko J Shiru Theory Rido 4-to Ippon Ukoaki, /-7lJt Kosho Yume 5 Do, Cover (J line - Den' - Line Ei 141σ) Organo Bolino Self Kizano σ) Revised 7Jj for °C Park Each inspection i・
” Result - Mercap 1 No (1ζ゛r10,000 Ru if Nobori I/LJ Kisano and Hi'Nirno, l+7 ≧ Self Surgano Bolino IJ-1-Duno [) becomes 11! In 1 evening - this vinyl + 'g' + 5 (IA group J nobori iy u *-g) as special c21) jj, 'un♂' + A: is Ihj
Sanoshi I Koichi Oruno j NovorishirokinanwomJItl
If L-mercapto is selected from at least two mercaptoalkyl 11 (including r) organoxane groups represented by the above formula, this product can be 1
Ultraviolet irradiation for more than a second or several Mr.
By irradiating the city with F-rays, it is easy and quick to create a rubber elastic film with no surface tack.
When you learn, when you find out, [Ni Koyo 5 C 2 and 1 is added, ・The rational body has an extension rate of 50, for example.
0% σ] - In addition, one hardening of 118" increases iL:t to J1, and the durability is 117 J'. - It has excellent durability.
The present invention was completed after confirming that there was no deterioration of physical properties due to aging during external exposure.

In the present invention σ) As the A) l component constituting the acid compound σ)
7 Reganoboj] 1 The formula shown in Norogisan is θ] (Heko σIJ(', + R2+
R3Q, methyl group, ethyl group-glopyl group, etc. θ]1
Aryl groups such as lukyrno, phenyldi1, etc.
Zyl groups, etc. are exemplified by alkarylno, (, etc.).
It is also different.) φσ) It is said to be a monovalent hydrocarbon 4-group, but it is necessary that the molecular chain is polyvinyl J, (and moon rainbow is 2t). a i++'
Autowork 2 Earthwork 2 and 3 - Also, this I + (directly this organoboriduroxano J) viscous 1 ■ at 25℃ C2: 30
~100,000 CS-I like this; ijj (fj 1
1 Convenience for mini-l') 5 (10~20
．． (The value may be set within the range of 1(lυcSσ).

In addition, as the B) component constituting the organopolysiloxane composition, σ) Mercagogue-alkyl group-containing orno-j-novolinologisan has a yu-xane single di-position represented by the general formula 14S R45lO in the molecule (contains two is also σ) and -1 (4 (emethyleno-ethylene-glopylene group-butylene group, etc. σ) Yotsuna alkyref) 4-R5 is a methyl group - ethyl group-alkyl group such as globyl group) is a fu L nyl group Aryl groups such as - vinylno, (-allylno, 1, etc. σ) alpnyl group - benzyl group, etc. valence σ) i1 tsuki base - b value is Ol[also +X
2). The general formula 〇〕1-noroxane single GZ such as σ) is 〒I■3 Its CHsio, US 03H6Si.19. ．．
1i (CJ(3)3(j13 ns c n 5i-o 11s c3r16sioo
, , -Cl-1° are exemplified. Since this σ)I3) component is in contrast to Orb 1 Novorizo 1J xane, which was expressed as a moon component in polyvinyl divination, the above-mentioned Shirogisanno 11 is 70) Molecule - LI Month 2 ′ν at least 211
It is necessary to have a viscosity of 5 to 500 eS (25° C.) and a viscosity of 1 (11 σ).

Organopolymer of the present invention; vinyl group-containing mercanoboriduloxane as component A) and mercanoboriduloxane containing vinyl group as component 13), mercanobori, 7u as component Uniform with Gizan C
2 mixture - It can be obtained by ``C2'', but the blending ratio of these is A) component 100 weight H'<To C2 - B)
Ingredients are 01 car: 4'1ll) or more and Q engineering ■] hardening j model with elasticity? 1 - I can't do this 5
If it is more than 0 parts, the deterioration of the elastic properties due to aging C2 will be significant and the initial rubber elasticity will not be obtained and the hard IW
However, the rubber properties are extremely poor.1
-A) component] -00!14. j,
It is necessary to range from 01 to 50 parts of component B for 2 parts of i and 2 parts of C.

However, within this blending range, a thickening agent known as component C) may be added to the A111 product (if the spinning is slow), The sensitizing Y111 includes acetophenonoglopionphenone-penzophenono, gysanotone, fluorenone, hensaldehydefluorene-anthraquinone-1.) nophenylamin-rubazole-3-methyl-1cetophenone,
Examples include 4-ri-a-mouth/diphenono-4-ethylbenzophenone-4-hydroxybenzophenone-bensoin-benzoin ethyl ether 71z-Michler ketone and the like. Depending on the curing speed, etc., jlN (2 may be determined - approximately 100 parts of the above-mentioned A) component;
Jt:, 2H gun code and j- are good. - This organoborinologisanocultivate also requires the addition of an oxidizing agent such as hydroquinone, which acts as a pot life extender, in the range of 50-1,0001) p.m. It may also be used as a diorganopolynoloxanol colorant-filling agent, and as a tinsotropic agent, finely powdered silica-oxidized carbon black-litopone.

In addition, JTF powder, etc., plasticizer, expansion milling stabilizer, adhesion promoter, adhesive, etc. may be added.

In addition, this organopolymiloxane fd, f IJ5L
For J, it is used as a solvent-free version (σ), but it may be added with a solvent depending on the situation - such solvents include hexane, hebutane, etc. For aliphatic hydrocarbons - benzene, etc. Toluene-quidrenatoσ' M
Examples include aromatic hydrocarbons) 4-octachloromethylene, trichloride hydrocarbons such as ethylene, esters such as ethyl acetate-butyl acetate, and ketones such as methyl ethyl ketone and acetone.

The organoleptic composition of the present invention can be easily and quickly cured by light (ultraviolet light) or electronic thermal irradiation, for example, ultraviolet irradiation for 10 seconds or less or electric thermal irradiation for 5 Mrad or less. The light source used for this is a xenon lamp rich in ultraviolet wavelengths, a low-pressure, medium-pressure, commercial mercury lamp, and a bump graph type for curing. 50 to 1.000 KeV, preferably 100 to 300 KeV, emitted from four small electron beam accelerators: , resonant transformer type, old linear type, Dynamigron fast type, and 11:11 + 'J wave type. It is better to use 4PJj! which has +1' (output per length is 80 to 1
At 60 W/cm, the generated wavelength is 365y1. +n is the dominant wavelength of 230-45 (it is best to use a wavelength range up to Jnm, and the irradiation time is generally less than a few papers, but it can be short to avoid being affected by heat. Preferably, therefore, a lower irradiation time of 10 seconds is preferred.

The spot beam is irradiated at the same speed as the line C, but it is sufficient to irradiate it with a linear filament or a continuous car-shaped beam, and the ultraviolet angle ρ1
[GOW'/11nσ] The range of irradiation for 1 second or less per lamp 11) may be sufficient. In addition, 0, 1~]
01vf i]d and the range h is sufficient.

This invention σ] Orukappori i/LI Kizanobu I [Nari I Riha] binary 4:! , 1'4','C' with l, so it can be widely used in various divine areas;
For example, is it useful as a ``Ten Air Insulation Leaf σ'' Bocchiingui A-Grintono, (XJy Coach/R Noguire Glass Three-Saw Insulation)'-F Glow Construction No~ringei Ka, etc.? Coating on glassic group;
Furthermore, it is stripped f1811! j! It can also be used as l - any sigma) in case of mechanical properties on the branched surface 111.
- Copper thermal Ichiro 115'', properties - Go A 5i1' with excellent water resistance, etc. - It has the advantage of being able to form a cured film with properties.

Next, two examples of the present invention will be described. Among the examples, the viscosity is the measured value at 25°C.

Example J Both ends are 1. IJ vinylsilyl group-chained dimethylbo+1 v loxane 9 with a viscosity of 10,000 cS
5:'d)+1- (H8CH'OHOII)(CT
I) 2 2 2 in SiO indicates yloginanno, (1oIIIl in min P!
Contains I - both ends are trimethyllinyl groups, and month≦Ll
75 parts of methylborinoloxa with gutgropyr group a, viscosity of 25 cSσ - 15 g of uncontained Norica
A small amount of 4-ethylbenzophenone and 500 p, pm of hydroquinone were passed through three tubes 22 times to prepare 11 organoduroxane compositions.

Next, σ) Composition: Form the decoy into a sheet with a thickness of 2.
When this was irradiated with ultraviolet rays from a pressurized mercury lug (] 6 U W/cm ) from a distance of 80 m for 1.0 sa. After applying I11, it became 1y-I, which has an elasticity with a 'trend' as shown in 1S.

- In the above, 4-ethylbenozophenone is la-
Add f2 without adding (thickness 2 eggs σ made from 1t composition),
/-1-1 When irradiated with 2 Mrad θ] two rays from a two-low-r4 Rugi electric accelerator (A Rugi sir (s=Nosune) fissure), this also produced an excellent elastic notebook, and this Add two C in Table 1 to t7'+ 41
Of course it showed L.

For comparison, instead of i2 methylpolynoroxane in ζ2, both ends j: j, : are vinyldimethylsilyl groups, (dimethyl blocked with) Uxane 1V1 position 995 mol% - Vinyl dimethyl, 7(,1 quinane medium 0
5 molar viscosity is 1 (1,000 C8 dimethylpolysiloxane (Comparative Example 1) - 7 dimethyl with vinyldimethylsilyl groups at both ends, /IJ xane unit is 995 mol % - vinyl methyl Siloxane claims are 0.
Methivinylborisiloxano (Comparative Example 2) with a viscosity of 1 (LO00e S) at 5 mol% and dimethyldirogisane whose both ends are capped with vinyldimethylsilyl groups and 95.0 mol% -vinylmethylsilogisane. Single (M is 50
Methyl vinyl polyv with 0 mol% viscosity tO,ooocS
/ U-xane (Comparative Example 3) was prepared in the same manner as described in Section 2. A U-xane composition was prepared in the same manner as in Section 2. This was made into a sheet with a thickness of 2.
What happened when irradiated with an electron beam? The physical properties of the cured product were as listed in Table 1.

Akira 4111; n6↑ of ji; (no history in a) Example 2 Both non-explained 17 and 97 moles of dimethylsiloxane at the 111-position were blocked with a divinylmethylsilyl group, in diphenylsiloxane (II: 3 moles) One person in charge roars, one stick is 5, O
D Oc 5OIJf ruphenyl vinyl, / U Gisanura personal property c + s = 1 + - 2 - Both ends are capped with trimethylnoryl groups - mercagtogropyl (methyl) siloxane unit 50 moles, dimethyl norogisane medium 50 moles Narugoku, 1 is 50 eS mercaptoalkyl fundamental tone, 8 parts of polyololoxane - TAX, 15 parts of lyca - 50 pl of hydroquinone, :) I
ll and 2 parts of benzene ethyl ether as a conventional method were added to prepare an organologisan compound, which was formed into a sheet with a thickness of 2 mm and then carried out (; When the product was irradiated with C2 ultraviolet rays in the same manner as II 1, it became a rubber elastic body having physical properties as shown in Table 2, C2.

In addition, in ``-'', sensitization 4'' is not added. When electron beam irradiation was performed, a comb elastic body was obtained in this case as well, and the physical properties as shown in Section 2k were lost.

Table 2 Example 3 Both ends were blocked with trivinylsilyl water, viscosity was 3,
0υυaSO) dimethylpolysilochitin 95, 044.

5 parts of Mercagtog U-pyl group-containing methylpolysilochitin having 5 siloxane groups in the molecule, capped at both ends with trimethylsilyl groups, and having a viscosity of 15 cS per unit.

Hydroquinone 500ppm and 1 as sensitizer
- Uniformly mixed 72 pieces of organopolynitoloxane and 11 pieces! To 100 parts of this composition was added 12 parts of fine powder and passed through a triple roll twice to prepare a noricorn rubber composition (sample 4).

Next, this sample 3-4 was filled with air *11] and then filled with two Kanko tubes and stored at room temperature for one month.
All of these did not increase in viscosity and did not gel.Take them out of the tube and kneel them in the air. As a result, it became a rubber elastic body with no tack on its surface - and when it was taken out of this tube and exposed to sunlight for 5 minutes, it became a rubber elastic body with no surface tack - an engraving of this clear pH book (no change in content) When the physical properties of the rubber elastic body were measured, the results were as shown in Table 3.

Table 3: Mt+Example 4 Both ends are blocked with trivinylsilyl groups, and the viscosity 1w is 3. fJ U Ocs' methylphenylpolysiloxane foam 1() o capital 1mi formula 0
H3 (us(OH2-+T-) sio -c' mercaptopropyl group-containing methylpolysilochitin having 1υ c14f units in the molecule and having a viscosity of 17 cs at 24% market weight between methoxy groups 10 notes L hydroquinone 5
00 ppm and 2 parts of benzoin ethyl ether as a sensitizer were added and mixed homogeneously to prepare an organonoloxane composition.

Next, apply this acid to a polyethylene laminated paper with a coating thickness of 0.8 μm (bi-uniformly).
When this coated surface C2 was irradiated with ultraviolet rays for 1.0 seconds in the same manner as in Example 1, 1 a hard film with no surface tackiness and 1 roughness was observed. When the peeling performance of the film was examined, it was found that it had excellent peeling properties and had good adhesion to polyethylene laminate paper due to the alkoxy groups contained therein, and did not fall off even when the film surface was rubbed.

In addition, in Section 2, a composition without a sensitizer was coated on C-nipolyethylene laminated paper in the same manner as above and irradiated with an electron beam in the same manner as in Example 1. The coated surface became a cured film with rubber elasticity without surface tack, and showed physical properties similar to those described above.

I-l"1.t'lRecipient: Jin-Etsu Chemical Yugyo (l, Ceremony Company Procedure Sleeve Book 1 ・1.1 Manual Patent Application No. 21tJ544 No. 21, 1988 2, Name of Invention Curable Olga Novolisiloxane 11 Composite 3 Name that corrects the name 1 1 and 1] Patent Dejima 11 name (20
6) Hakuetsu Chemical Industrial Forestry Company 4 Agent Address: 103 Higashib (Tokyo Chuo 1/■) 4-9 Motohashihonmachi Date of Shipment: 11C February 28, 1959 Details@Page 1, 2 There are differences between pages 3, 4, 17, 19, and 21 negative typed as shown in the attached sheet.

Claims (1)

[Claims] ], A) In the formula \ to RI, R21 and 3 are the same or! 4 divine vesicles i 11 monovalents that do not contain bonds! Organopolysiloxane in which the molecular chain rice cultivation is chained with polyvinyl groups 100 cities jI
t el (B) general formula (5% formula%) ＼R is a/, I<Kylene thread, R is a monovalent organic system, b
is U, ] or 2) Mercaptoalkyl group-containing organopolysiloxane having at least two silochitin units in the molecule 01-50 Ft part C) Sensitizer
A curable organopolysiloxane composition characterized in that it has a curable organopolysiloxane composition of 0 to 113 stones) and 1 to 1 stone.