JPS6195069A - Novel two-component curable silicone 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 Richard P. Etzkberg, filed on the same date as this application and assigned to the assignee of this invention.
See co-pending U.S. patent application Ser.

BACKGROUND OF THE INVENTION The present invention relates generally to compositions that can be cured by two different mechanisms, and more particularly to a combination of a free radical-catalyzed UV-hydrosilation reaction and a platinum-catalyzed thermal hydrosilation reaction. It relates to a composition that is cured by both.

Silicone compositions are becoming widely popular as protective coatings for electronic components mounted on circuit boards. Silicones are ideal for this purpose because of their moisture resistance, thermal stability and resistance. Silicone compatible coatings that have been developed are thermosetting and provided in the form of solutions in organic solvents.

However, in addition to safety and environmental concerns, energy costs
') The high cost has led to the development of alternative technologies such as silicone compatible coatings that can be cured by UV light.

Both heat-curable and UV-curable silicone compatible coatings have several drawbacks. The use of thermosetting compliant coatings risks damaging fragile and heat-sensitive electronic components, resulting in excessively long thermal curing cycles and, as a result, reduced productivity of coated circuit boards. Radiation-curable silicone compliant coatings, on the other hand, allow for faster processing speeds and avoid damage to electronic components, but the compatibility coating is often not fully formed due to the so-called "shadow effect." Simply put, this shadow effect occurs when elements placed on a circuit board protrude from the optical surface of the board, creating shadows and thus preventing effective curing. Although this shadow effect can be largely overcome by using UV light, there can be cracks and the like where ultraviolet light cannot easily penetrate and therefore the CUV-curable composition cannot be cured.

In view of the above, in order to overcome the above-mentioned drawbacks, UV
It would be highly desirable for those skilled in the art to obtain compositions that are both curable and thermally curable (either at room or elevated temperatures).

It would also be desirable if such compositions could be utilized in other applications, such as as silicone release coatings.

Platinum-catalyzed addition-curable silicone compositions are well known in the art. For example, Grenople
ble) U.S. Patent No. 3904 Otsu 77 includes (1)
A coating composition made from a vinyl-terminated polysiloxane, (2) a hydrogen-containing polysiloxane, and a platinum catalyst effective to effect the copolymerization of (31(1) and (2)) is applied to a flexible sheet. By coating the material,
It is not disclosed that the sheet material can be made non-adhesive to surfaces that would normally adhere to the sheet material.

Another variation of such a technique is the Eckbe
rg) in U.S. Patent No. 41. ．． 2J6sr No. 70 and No. 6
It is disclosed in 3ri4j4t7. Both of these patents are assigned to the assignee of the present invention and are incorporated by reference into this disclosure.

U.S. Patent No. 31 to Qhto et al.
No. tr discloses a photopolymerizable composition containing at least one organopolysiloxane having an unsaturated group of the following formula.

Here, R' is a hydrogen atom, a phenyl group, or a phenyl group substituted with a halogen, and R2 is a hydrogen atom or a methyl group. Examples of such radicals are acryloxy, methacryloxy, cinnamoyloxy or halogenated cinnamoyloxy.

U.S. Patent No. 4724 to Berger et al.
No. 710@- discloses a composition comprising a polyorganosiloxane containing vinyl groups and having a sensitizer, which can be cured by exposure to high intensity ultraviolet light.

A silicone elastomer composition suitable for ultraviolet curing disclosed in U.S. Pat. )2 R
'StO÷RSiO piece StR' (C1(s)
2 (wherein R' represents hydrogen or a monovalent radical selected from methyl, vinyl and hydroxy; R represents hydrogen or a substituted or unsubstituted monovalent hydrocarbon group;
θ0.2 to 4t9j% of the total number of groups R1 and R2 are vinyl groups, and θO to the total number of groups R1 and 82
Gu99! (B) 65 to 70 parts by weight of a polyorganosiloxane having the following formula: (R1)b (CH2=CH)aSiO4-a-62 "11 (Here, R5 is a substituted or unsubstituted monovalent hydrocarbon group other than vinyl, a represents the number of 00/xb/ on average, and b represents the number of θxbx3 on average. represents the number of a+b
07 to 70 parts by weight of a peroxyester of the following formula: R-0-0-C-R5 (where R4 is a substituted or unsubstituted monovalent fatty acid) (15 is a substituted or unsubstituted monovalent aromatic group).

/9 and 3 years? Eckberg et al., U.S. patent application no. The ultraviolet curable composition disclosed in No. 2z2ri No. 9 contains (A)
is hydrogen or a C1-8 alkyl group, R' is hydrogen,
Diorganoporin loxane consisting of units of C1-8 furkyl group or monovalent mercaptoalkoxyalkyl functional organic group of 2 to θ carbon atoms, (B) having the formula (C
H,=CH)RnSin(,-n)72(However, R
is hydrogen or a C1-8 alkyl group, and n has a value of 0-J).
(C) a catalytic amount of a photoinitiator.

However, to the best of the applicant's knowledge, both free radical-catalyzed UV hydrosilation reactions and platinum-catalyzed hydrosilation reactions cure;
Therefore, no silicone composition is disclosed or suggested anywhere that avoids the drawbacks of compositions that cure by only one of the aforementioned mechanisms.

SUMMARY OF THE INVENTION Seven objects of the present invention are the free radical catalyzed U
It is an object of the present invention to provide a composition that is curable by both a V-hydrosilation reaction and a platinum-catalyzed hydrosilation reaction.

Another object of the present invention is to provide an article having the above composition cured on a circuit board or the like.

Another object of the invention is to provide a method for making the compositions and articles described above.

The curable composition provided according to the present invention has the following (A) to
Consists of (F).

(A) A polysiloxane having the following general formula: where each R is independently selected and is a substituted or unsubstituted monovalent hydrocarbon group having from/to 20 carbon atoms; R1 is hydrogen; a hydroxyl group, or a substituted or unsubstituted hydrocarbon or hydrocarbon oxy group having /~coθ carbon atoms, R2 is a lower alkenyl group, and X is an alkenyl-containing siloxy unit containing about y is a number such that the hydrogen-containing siloxy unit is approximately θ! ~about! (+y+z) is a number such that the viscosity of the polysiloxane is from about 2! centipoise to about 2J04 θθθ centipoise at 2J-'C.

(B) Free radical type photoinitiator.

(C) A hydrosilation catalyst of or containing a noble metal.

(D) Optionally, an organohydrogen polysiloxane.

(E) Optionally, an olefin-containing polydiorganosiloxane.

(F) Optionally, inhibitors.

DESCRIPTION OF THE INVENTION Broadly speaking, the present invention provides a method for preparing both a photoinitiator or photocatalyst and a noble metal or noble metal-containing hydrosilation catalyst having a silicon-bonded hydrogen atom and a silicon-bonded alkenyl group (preferably a vinyl group). including adding it to a curable composition. The silicon-bonded hydrogen atoms and silicon-bonded alkenyl groups can be on the same or different polysiloxane chains. For the present invention
0 What is essential is that silicon-bonded hydrogen atoms and silicon-bonded alkenyl groups crosslink when exposed to ultraviolet light due to the presence of a photocatalyst, and that silicon-bonded hydrogen atoms and silicon-bonded alkenyl groups are crosslinked due to the presence of a noble metal catalyst or noble metal-containing catalyst. The hydrogen atom and silicon-bonded alkenyl group crosslink at room temperature or high temperature.

In preferred/specific examples of the present invention, a curable composition consisting of the following (A) to (F) is obtained.

(A) A polysiloxane having the following general formula: where each R is an independently selected carbon atom from / to 20
R1 is a substituted or unsubstituted monovalent hydrocarbon group having a hydrogen atom, a hydroxyl group, or a carbon atom
R2 is a lower alkenyl group, and X is a number such that about θ/ to about 2θ moles of alkenyl-containing siloxy units are present; y is approximately θ of hydrogen-containing siloxy units! ~about! The viscosity of this polysiloxane is approximately 2! Centipores ~ approx. 2J″oo
, ooo centipoise.

(B) Free radical type photoinitiator.

(C) Noble metal or noble metal-containing hydrosilation catalyst.

(D) Optionally, an organohydrogen polysiloxane.

(E) Optionally, an olefin-containing polydiorganosiloxane.

(F) In some cases, inhibitors.

The polysiloxane (A) of the present invention is represented by the above formula (I). In formula (I), the group R may be any substituted or unsubstituted hydrocarbon group having / to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and decyl. alkyl groups such as vinyl and allyl, cycloalkyl groups such as cyclohexyl and cycloheptyl, aryl groups such as phenyl, aralkyl groups such as β-phenylethyl, and hydrogen atoms of these groups. Part or all of 3. is a halogen atom such as fluorine, chlorine or bromine, a cyanoethyl group, or 3.
3. Any group substituted with a 3-trifluoropropyl group. From the standpoint of availability and ease of synthesis, it is preferred that almost all R groups be methyl or methyl and phenyl.

The group R1 may be any of the R groups mentioned above and may also be a hydrogen atom, a hydroxy group or a hydrocarbon oxy group having / to 20 carbon atoms such as methoxy, ethoxy or propoxy. R2 is vinyl, allyl, propenyl,
It can be any lower alkenyl group such as butenyl, and most preferably R2 is vinyl.

What is important is that polysiloxane (A) contains a silicon-bonded vinyl group and a silicon-bonded hydrogen atom in the same molecule. The number of vinyl-containing siloxy units is usually about 0/- to about 20 moles based on the total number of siloxy units in polysiloxane (A). In addition, generally the number of hydrogen-containing siloxy units is approximately θ! with respect to the total number of siloxy units in the polysiloxane (A)! ~about! It is θ morti.

It will be understood by those skilled in the art that the values of X and y in the formula (D may be zero, provided that R1 is vinyl or hydrogen, respectively. It is also possible to use mixtures of polysiloxanes in which hydrogen is present only at the ends and vinyl groups are present only on one polymer chain. Other variations will be apparent to those skilled in the art.

For example, vinyl-containing siloxy units and/or hydrogen-containing siloxy units may be present both on a polymer chain and at a chain termination moiety.

If the number of vinyl groups or hydrogen atoms bonded to silicon is less than the above ranges, the adhesive ability of the cured composition will be reduced. If the number of these substituents exceeds the above range, the heat resistance will be reduced or the curing rate will be inadequate. If the polysiloxane (A) contains silicon-bonded hydrogen atoms and silicon-bonded vinyl groups within the above-mentioned range, bubbles will not be generated due to the generation of hydrogen gas when exposed to ultraviolet rays, and the composition will be After brief exposure of the article to UV radiation, it hardens sufficiently so that it can be placed anywhere to heat cure the coated article. Thermal curing for purposes of this application includes subjecting the composition to elevated temperatures or simply allowing a noble metal catalyzed hydrosilation reaction to occur at room temperature.

The number of diorganosiloxy groups present in the polysiloxane (A) is not critical and ranges from 0 to about 95! gMole〇Any value is acceptable. Generally, the viscosity of polysiloxane (A) is about 2 at 2J℃! Centipoise ~ approx. 2600. θ00
There should be enough diorganosiloxy units to be centipoise.

In addition to the bifunctional units exemplified in formula (I),
It will be understood by those skilled in the art that trifunctional siloxy units of 1, , (R as previously defined) and/or tetrafunctional siloxy units of the formula 5in20 may be present.

The number, if any, of such units to use will depend on the particular application contemplated and will be readily determined by one skilled in the art without undue experimentation.

In preferred/embodiments of the invention, the vinyl-containing siloxy units are about 10 to about 10. About 2.0 to about 20 θ moles of hydrogen-containing siloxy units are present, and the viscosity of the polysiloxane (A) is 2! Approximately 100 centipoise in °C
It is approximately 10,000 centipoise.

Free radical type photoinitiators or photocatalysts are well known in the industry. The photoinitiator (B) of the present invention may be any known free radical-type photoinitiator that is effective in inducing crosslinking between silicon-bonded vinyl groups and silicon-bonded hydrogen atoms.

A particularly preferred photoinitiator for practicing the present invention is the photoinitiator disclosed in U.S. Patent No. zrz63 by Hatanaka et al.
No. 1, filed on April 2, 7913, and assigned to the assignee of this invention.
) et al., U.S. Patent Application No. 627,292. The teachings of this patent and patent application relating to photoinitiators are incorporated by reference into this application.

In summary, Eckberg et al. disclose certain perbenzoic acid esters having the following general formula (II): where 13 is a monovalent alkyl or aryl group and 2 is hydrogen, alkyl, /X is rogen, nitro, amino or amide. The nature of substituent 2 influences the stability of the peroxy bond. That is, electron-deficient substituents stabilize peroxy bonds, and electron-rich substituents increase the reactivity of peroxy bonds. These perbenzoic acid esters react benzoyl halides with hydroperoxides (Blomquist
) and Berstein's Journal of the American Chemical Society (J, A.
mer, Chem, Soc,), Volume 73, No. tt
It can be synthesized by a known method such as the paper on page 4tt (/9!/). Preferred perbenzoic acid esters include t-butylperbenzoate and its para-substituted derivatives, namely t-butylperu p-nitrobenzoate, t-butylperu p-methoxybenzoate, t-
Included are butylperu p-methylbenzoate and t-butylperu p-chlorobenzoate.

The amount of photoinitiator used is not critical as long as proper crosslinking is achieved. It is preferred to use the smallest effective amount of any catalyst possible. Generally, the amount of photoinitiator is [about θ/~10 parts by weight per 100 parts by weight of polysiloxane (A)]
Any amount of parts by weight may be used. Preferably, the photoinitiator concentration is from about 1 to about 1 part by weight per 100 parts by weight of polysiloxane (A).

In addition to t-butyl perbenzoate and its derivatives as photoinitiators, nick barb (') Eckberg
) disclose that inclusion of a certain photosensitizer increases reactivity. Such photosensitizers are Ph
-C- chromophore (Ph is phenyl) and at least two benzene rings (which may be fused,
Polyaromatic compounds having organic groups or cross-linked with hetero groups such as oxa, thio, etc.

Preferred photosensitizers are benzophenone and t-butylanthraquinone.

Other photoinitiators include U.S. Pat. No. 32.5″9JO7;
No. 396 and 30 evening issue, No. 396≦, jf73, No./
/3! Ri No. 2, No. 34! Kota issue, No. 6310. Otsu θ
θ, No. 63 Da, and No. 4TT2, and those skilled in the art can easily determine whether it is appropriate for use in a particular situation. The teachings regarding photoinitiators of all of the above patents are incorporated herein by reference.

Component (C) can be any noble metal or noble metal-containing catalyst effective to initiate a thermal hydrosilation curing reaction. In particular, all well-known platinum and rhodium catalysts useful for catalyzing addition reactions between silicon-bonded hydrogen atoms and silicon-bonded olefinic groups are included. Platinum or platinum-containing complexes are the most preferred noble metal catalysts, examples include platinum metal supported on charcoal, 7 Ashby No. 11
3 patents, 1 isztoi and 3/! 9.6t2
The platinum-hydrocarbon complex described in No. 5 Lamo
The platinum-alcoholate catalyst described in U.S. Pat.
rstedt) U.S. Patent No. 3. ? /4t, 73θ
platinum complexes described in this issue, as well as Modic
platinum chloride described in U.S. Patent No. 35/O, No. 9G of )
There are olefin complexes. All of the above US patents relating to platinum or platinum-containing catalysts are incorporated herein by reference.

The most preferred catalyst for facilitating the thermal hydrosilation reaction is disclosed in U.S. Patent No. 3. /39. This is the Ashby catalyst described in the tθ/ issue.
Other platinum metal or platinum-containing catalysts that can be used in the present invention are well known to those skilled in the art.

Hydrosilation catalysts other than those based on platinum can also be used to effect thermal curing.

For example, complexes of metals such as rhodium, ruthenium, palladium, osmium and iridium can be utilized. Of the non-platinum based catalysts, those based on rhodium are most preferred. Preferred rhodium catalyst preparations and types are described by Eckberg.
), US Pat. No. 107, also incorporated herein by reference.

As with the photoinitiator (B), the amount of noble metal or noble metal-containing catalyst (C) is not critical as long as proper crosslinking is achieved. In the case of Okuya, the amount of noble metal or noble metal-containing catalyst is about 10 to about 10 to about 100% metal atoms per polysiloxane (A). θOppm. It may be desirable to use higher amounts of catalyst (C) when organohydrogen polysiloxanes (D) and vinyl-containing polysiloxanes (E) are optionally included. Of course, suitable amounts of catalysts (B) and (C) can be determined by those skilled in the art without undue experimentation. It will also be understood by those skilled in the art that it is within the scope of the invention to use mixtures of various photocatalysts and noble metal or noble metal-containing catalysts.

The organohydrogensiloxane (D) can be any of the fluids, resins, or mixtures thereof utilized by those skilled in the art as crosslinking agents in addition-curable silicone systems.

Particularly useful organohydrogen polysiloxanes in the practice of this invention have from about 10% to 100% SiH groups with the remaining groups being dimethylsiloxy units and having about 10%
．． A trimethyl-terminated polymethylhydrogen siloxane fluid having a viscosity ranging from about 1000 centipoise to about 1000 centipoise. However, any organohydrogenpolysiloxane having the following general formula is within the scope of this invention.

(1) RaHbSi04-a-b +1. i Such organohydrogen polysiloxanes are disclosed in, for example, U.S. Pat.
Both of these are well known in the art, as described in the disclosure herein.

Groups included in R in formula (1) include alkyl such as methyl, ethyl and propyl, cycloalkyl such as cyclopentyl, cyclohexyl and cycloheptyl, aryl such as phenyl, naphthyl, tolyl and xylyl, and phenylethyl. and aralkyl, such as phenylpropyl, and substituted groups of the foregoing, such as halogen-substituted and cyanoalkyl-substituted versions.

Other organohydrogenpolysiloxane fluids are well known in the industry, including U.S. Pat. /Yu issue (also incorporated herein by reference).

Organohydrogen polysiloxane resins can be utilized in place of or in conjunction with organohydrogenpolysiloxane fluids. Such organohydrogenpolysiloxane resins are well known in the industry, as described, for example, in Jeram, U.S. Pat. . In summary, organohydrogen polysiloxane resins have RH-8iOo,5 units and 5i02 units (where R+H units vs. 5in
The ratio of 2 units is in the range 1O-47 and R is as defined previously) or 8 H-Sin, 5 units, R25iO units and Sin2 units (where R
The ratio of +H units to S i02 units is /2~. 2.0 and R is as defined above).

When organohydrogenpolysiloxanes are used, they can be used in any amount so as to obtain specific properties in the cured product. Generally, about 10.0% per 100 parts by weight of polysiloxane CAB. Parts by weight ~ approx. 10. It should be used within the range of parts by weight.

An optional further component for the practice of this invention is an olefin-containing polydiorganosiloxane (E).

Like the organohydrogenpolysiloxane (D), the olefin-containing polydiorganosiloxane (E) can be either a fluid or a resin or a mixture thereof. Most preferably component (E) is a vinyl-containing polydiorganosiloxane.

A typical vinyl-containing polydiorganosiloxane fluid has the formula: where R is as previously defined, R is a group having fullkenyl unsaturation, preferably vinyl, and a and b are linked at this vinyl. K is a positive integer such that the terminated polysiloxane has up to about 20 weight groups of R4 groups. The viscosities of such polysiloxanes range from about 23" C. to about 100.00 θ centipoise. These polysiloxane fluids are also available from Grenoble and Nick Barb.
Eckberg) U.S. Patent No. 6? It is described in No. 73.

Vinyl-containing silicone resins may also be used, such as Jerum (Jerum).
Am) is well known in the industry as described in the US Pat. Generally, these resins are resins having ViR, SiO, units and Si02 units (where the ratio of hydrocarbon substituents to Si is 07-4
7)? jrabiKViR2SiO0,5 units, R25IO
and resins having S io2 units where the ratio of hydrocarbon substituents to Si is θ?~, 2.4t. More specific details regarding these resins and their manufacture can be found in Jer.
“)0 Patent No. 0″/, 0/0 reference
·)sea bream.

Vinyl-containing polysiloxanes can be used in any amount in the present invention. It should be noted that those in the trade will be aware that placing precious metals or precious metal-containing catalysts (C) in the same packaging as polysiloxanes (A) will result in gelling or hardening of the product before it reaches the consumer. . Therefore, for commercial use, olefin-containing polysiloxanes (E) are useful as supports for the primary noble metal catalysts (C). That is, in preferred/embodiments of the invention, the curable composition is provided in two or more packages. Seven packages contain the vinyl-containing polysiloxane, precious metal catalyst, and optionally an inhibitor, and another package contains the remaining ingredients. Such two package systems are well known in the industry. A particularly preferred multi-component packaging system is the Grenoble
) and Nick Barb (Eckberg) U.S. Patent No. 4t4tjr/! can be obtained by applying the teachings of No.

Inhibitor (F) to extend the pot life of the compositions of the invention
It is also contemplated that the curable composition may include: Seven examples of suitable inhibitors include Eckb
erg), U.S. Pat.

Nick Barb (Eckberg) US Patent No. 4
No. 1.2t210.7 lists other suitable inhibitor compounds such as certain acetylenic compounds, olefinic carboxylic acid esters of aliphatic alcohols such as vinyl acetate, alkenyl isocyanurates and mixtures thereof. is disclosed.

Eckberg U.S. patent application Ser. , discloses that blends of dicarboxylic esters with carbon-carbon unsaturation and olefinic carboxylic esters of aliphatic alcohols are particularly effective as inhibitors. The Eckberg patents and patent applications cited above are each incorporated herein by reference.

In another aspect of the present invention, methods of making the curable compositions of the present invention and articles having the cured compositions on their surfaces are provided.

To produce the curable compositions of the present invention, the various ingredients are simply brought together or packages containing the various ingredients are mixed. To make articles of the present invention, the compositions of the present invention may be applied to substrates such as circuit boards if the composition is intended to be used as a conformable coating, or to Mylar if the composition is to be used as a releasable coating. (My
by applying the composition to a flexible sheet material, such as paper or paper, then exposing the coated substrate to sufficient ultraviolet light to harden the composition, and finally bringing the article to room temperature or elevated temperature. Complete curing. Of course, the higher the temperature, the faster complete curing will occur.

The following examples are provided by way of illustration and not limitation to enable those skilled in the art to better practice the invention. All parts are by weight unless otherwise specified.

Examples / A silicone terpolymer (designated Polymer A) was prepared by acid-catalyzed equilibration of polymethylhydrogensiloxane, Sym-tetramethyl-tetravinyl-cyclotetrasiloxane and octamethylcyclotetrasiloxane.

The resulting polymer contains approximately methylhydrogensiloxy units! % by weight, about 7% by weight of methylvinylsiloxy units, and about 1r% by weight of dimethylsiloxy units, and 2! The viscosity in °C is /? θθ centipoise. 2. Add benzophenone to this fluid. ! % by weight, butyl perbenzoate was prepared by θ weight. Next, the polymer-containing/photocatalyst blend/30 El was combined with 7 g of 2 centipoise organohydrogen polysiloxane resin. The resulting polymer-containing/photocatalyst/organohydrogen - Two parts of the polysiloxane resin blend are then added to a 376% solution of the vinyl MQ resin as a platinum-octyl alcohol complex in a 376% solution of linear dimethylvinylsiloxy chain terminated polydimethylsiloxane fluid. Solvent WL with 5 ppm and 0.7% diallyl maleate inhibitor
/ part.

This 92/blend is the curable composition of the present invention.
The coating bath of this composition is a clear freshwater color and contains a total of 2 to jppm of platinum metal as platinum complex catalyst, t-
Butyl perbenzonitos! Note that it contains % by weight and benzophenone catalyst, L2J-% by weight.

This curable composition was manually applied to a polyethylene or supercalendered kraft substrate and PPG model QC
The cure was qualitatively evaluated immediately after exposure to two medium pressure mercury lamp UV sources mounted on a moving conveyor in the /202AN processor. Curing was done in a nitrogen blanket. The results are shown in Table I.

Table I? Mill samples (experiment #1) were exposed to UV light for 77 hours! Allowed to stand at room temperature of °F. What did you observe there?
The mill film was completely cured over the entire cross section.

Example 2. 2! Centipoise organohydrogen polysiloxane resin! Polymer A10 obtained in Part and Example/. Blend of O part! I as Pt metal, 2'l ppm platinum flucorate catalyst, 10% t-butyl perbenzoate and penzophenone! A 373% solution of vinyl MQ resin dissolved in a linear dimethylvinylsiloxy chain-terminated polydimethylsiloxane fluid containing H! Blended with I. Thus, in transparent color, pt is about /,2 ppm,
T-butyl perbenzoate! A curable composition containing 1/2 of a benzophenone catalyst was obtained.

Coatings of this composition with a thickness of 100 mils on various substrates,
Exposure to UV radiation under various conditions. The results are listed in Table ■.

Table■ Next, when the partially cured compositions of Experiments/, C, and B were left in a dark place at room temperature for two days, it was observed that they were completely cured and adhered well to each substrate. It was done.

Example 3 This example simulates the shadow effect seen in coatings on circuit boards and other similar substrates. In this experiment, the curable composition of the present invention was applied to the thickness of a gummy coating on a stainless steel panel measuring 1/2 inch x 1 inch, and then an L-shaped 7 inch wide metal strip was passed over the coated panel and exposed to ultraviolet light. The composition effectively blocked the composition over a 7 inch wide strip. The coating was exposed to focused UV light at zero theta watts for 7 seconds in an air atmosphere.

The composition of this coating composition is as follows: Example/Polymer Ag part, General Electric Company (Qeneral Co., Ltd.)
Electric Company) is BS-￥30
Polymethylhydrogensiloxane/part sold under the trademark 0c, and as Pt metal, 2 ppm platinum complex and t-butyl perbenzoate 10S and penzophenone! 32! of vinyl MQ resin dissolved in a linear dimethylvinyl chain-terminated polydimethylsiloxane fluid containing Chi solution! It was the θ section. The results are shown in Table 1 as a function of time.

Thermal curing was carried out in the dark in a room source following UV exposure.

Table 1 Examples Filtrol in nitrogen atmosphere,
Trimethyl-terminated linear polydimethyl-methylhydrogensiloxane/60 in the presence of 70 g of 20 acidic clay catalyst
A terpolymer was produced by blending 1/3, sym-divinyltetramethyldisiloxane/3&, and octamethylcyclotetrasiloxane θg at 100° C. for 3 hours.

After filtering the obtained polymer, ito℃1.20! I
stripping under a vacuum of 200 centipoise//? , 2! I got it. This polymer was heated at 60°C.
The mixture was treated with a Benruff 1122 weight gauge while stirring gently. This material was designated as "bath a".

Next, 1 bath a10. [Bat bJ, and 90 parts by weight of bath a, and polymethylhydrogen siloxane fluid C,5LjOθθ]
, General Electric Co.
``Bat C'' was prepared, which consisted of 70 parts by weight of a mixture of 22% benzophenol (sold by Ctric Company) + 300 ppm of platinum complex catalyst (as platinum metal) and parts by weight of t-butylperpenezoate. did.
To study these compositions, apply these compositions by hand onto supercalendered kraft paper to a thickness of less than mil and expose the coating sheet to UV radiation or heat the coating sheet. Either in an air oven or both. The UV intensity is yoθ watts in the PPG Lab processor and the hot air oven is /! It was maintained at θ°C. Curing was qualitatively evaluated as a function of processor line speed and oven residence time. The results are shown in Table ■.

Table■ 20fprn Air - No migration.

A little dirty.

--6 seconds, no hardening.

--30 seconds, no curing.

c: 1100fp N2 - No transition.

No stains.

KokonJ,l:l,.

! θfpm Air - No migration.

A little dirty.

The coating composition (b) is /9. Benzophenone and t-butyl as described in Eckberg U.S. Pat. showed a synergistic effect of perbenzoate. The coating composition (C) contains a platinum-containing catalyst.
Contains approximately 30 ppm of gold metal, which is approximately 7 ppm after blending. It was observed to gel in minutes. Bath (C
) to approximately θ! It has been found that adding water increases the bath life to about 3 hours without any significant effect on UV or heat curing.

Next, baths (b) and (C) were mixed with acetone:hexane (/:/)
Make a 20% solution in a solvent and apply it to a mechanical laboratory coater. It was applied to #gθ super calendered kraft paper using a wire-wound rod.

The coating sheet was (1) 10. θ feet/min, (
2) In air - 0 ft/min, and 10 in air. UV processor (lamp output) in θ feet/min.

Watt) k through then open lIC10 at 730℃
I put it in for a second and it hardened. Bath (b) did not cure under conditions (3), but the other sheets were free of stains and migration. Then the cured sheet has a super calendar kraft backing! Laminated with mill adhesive coating. Make a 2 inch x ♂ inch tape from these laminates and pull it at a tensile speed of 7 minutes per second /♂θ
The force required to peel the silicone/SCK laminate from the adhesive/SCK laminate by pulling at an angle of .degree. was recorded. The quantitative peeling data thus obtained are shown in Table V.
Shown below.

play ■ b / , 20-3θ9 23-3θl
Ko! -3 evening Ib j 36-41.011
3 Taichi! Og gu O-! θIC/ Gu θ-! θ,!
i'! ! -4t3-11 30-g0gc
2 1.0-73; I guj-68gu θ-!
! gCJ riz-tsg coj-33920-30
The fact that the release force seems to decrease with aging for sheets coated with 9 "Bath C" may suggest that there is a 5 post-cure with a platinum catalyzed addition reaction after UV or heat treatment.

procedure? ff1. iE Book (Oo) 1. Case description 1985 Patent Application No. 212752 2. Title of the invention Novel dual-curing silicone composition 3. Person making the amendment Relationship with the case Applicant Location United States of America, 12305 , New York, 4, Agent Address: 4F, 3554 Wapil, 1-14-14 Akasaka, Minato-ku, Tokyo 107

Claims (47)

[Claims] (1) A curable composition containing a silicon-bonded hydrogen atom and a silicon-bonded olefinic group, the composition comprising at least one free radical photoinitiator and the silicon-bonded hydrogen atom. and at least one noble metal or noble metal-containing hydrosilation catalyst for crosslinking the silicon-bonded olefinic group. (2) (A) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, each R^ is a substituted or unsubstituted monovalent hydrocarbon having 1 to 20 independently selected carbon atoms. group, R^1 is hydrogen, a hydroxyl group, or a substituted or unsubstituted hydrocarbon or hydrocarbonoxy group having 1 to 20 carbon atoms, R^2 is a lower alkenyl group, and x is an alkenyl-containing group. y is a number such that about 0.1 to about 20 mole percent of siloxy units are present, y is a number such that about 0.5 to about 50 mole percent of hydrogen-containing siloxy units are present, and x+y+z is a Viscosity is about 2 at 25℃
5 centipoise to about 2,500,000 centipoise, (B) a free radical type photoinitiator, and (C) a noble metal or noble metal-containing hydrosilation catalyst. thing. (3) A composition according to claim 2, characterized in that almost all R groups are methyl or a mixture of methyl and phenyl. (4) The composition according to claim 2, wherein R^2 is vinyl. (5) x is about 1.0 to about 1 vinyl-containing siloxy unit;
0.0 mol% is present, y is a number such that about 2.0 to about 20.0 mol% of hydrogen-containing siloxy units are present, and x+y+z is the viscosity of the polysiloxane (A). is about 100 centipoise to about 10,000 at 25℃
Composition according to claim 2, characterized in that the number is centipoise. (6) Free radical type photoinitiators have a general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^3 is a monovalent alkyl or aryl group, and Z is hydrogen, alkyl, halogen, nitro , amino or amide). (7) The free radical type photoinitiator is t-butyl perbenzoate, t-butyl per-p-nitrobenzoate,
The composition according to claim 6, characterized in that it is selected from the group consisting of t-butyl per-p-methoxybenzoate, t-butyl per-p-methylbenzoate and t-butyl per-p-chlorobenzoate. . (8) The composition according to claim 7, wherein the free radical photoinitiator is t-butyl perbenzoate. (9) Free radical type photoinitiators furthermore have a ▲mathematical formula, chemical formula, table, etc.▼a chromophore (where Ph is phenyl), and are condensed or cross-linked with an organic group or a hetero group. 7. The composition according to claim 6, further comprising a sensitizer which is a polyaromatic compound having at least two benzene rings. (10) The composition according to claim 9, wherein the photosensitizer is t-butylanthraquinone. (11) The composition according to claim 1 or 2, wherein the noble metal or noble metal-containing hydrosilation catalyst is selected from the group consisting of platinum metal, platinum complexes, rhodium metal, and rhodium complexes. thing. (12) The free radical photoinitiator is polysiloxane (
A) is present in an amount of about 0.1 to about 10 parts by weight per 100 parts by weight, and the noble metal or noble metal-containing catalyst is present in an amount of about 10 ppm to about 500 parts as precious metal based on polysiloxane (A).
3. A composition according to claim 1 or 2, characterized in that the composition is present in an amount of pm. (13) The composition according to claim 2, further comprising an organohydrogen polysiloxane. (14) The composition according to claim 2, further comprising a vinyl-containing polysiloxane. (15) The composition according to claim 2, further comprising an organohydrogen polysiloxane and a vinyl-containing polysiloxane. (16) The composition according to claim 2 or 15, further comprising an inhibitor. (17) (A) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, almost all R is a methyl group or a mixture of methyl and phenyl groups, and R^1 is a hydrogen atom, a hydroxyl group, selected from the group consisting of methyl and methoxy groups, R^2 is a vinyl group, x is a number such that from about 10 to about 10.0 mole percent vinyl-containing siloxy units are present, and y is a hydrogen-containing group. The number of siloxy units is such that about 2.0 to about 20.0 mole percent is present, and x+y+z is such that the viscosity of this polysiloxane is about 1 at 25°C.
(B) 0.1 to 10 parts by weight per 100 parts by weight of (A) of t-butyl perbenzoate, t-butyl perbenzoate; -p-
a free radical type photoinitiator selected from the group consisting of nitrobenzoate, t-butyl per-p-methoxybenzoate, t-butyl per-p-methylbenzoate and chlorobenzoate; (C) 10 ppm as platinum metal relative to (A); ~50
A curable composition comprising 0 ppm of platinum metal or platinum-containing hydrosilation catalyst, (D) an organohydrogen polysiloxane, (E) a vinyl-containing polydiorganosiloxane, and (F) an inhibitor. (18) A method for producing a curable composition containing a silicon-bonded hydrogen atom and a silicon-bonded olefinic group, the composition comprising at least one free radical type photoinitiator and the silicon-bonded olefinic group. A method characterized in that at least one noble metal or noble metal-containing hydrosilation catalyst for crosslinking hydrogen atoms and the silicon-bonded olefinic group is added. (19) (A) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, each R represents one independently selected carbon atom.
It is a substituted or unsubstituted monovalent hydrocarbon group having ~20 atoms, and R^1 is hydrogen, a hydroxyl group, or one carbon atom
~20 substituted or unsubstituted hydrocarbon or hydrocarbonoxy groups, R^2 is a lower alkenyl group, and x is a number such that about 0.1 to about 20 mol% of alkenyl-containing siloxy units are present. where y is a number such that about 0.5 to 50 mol% of hydrogen-containing siloxy units are present, and x+y+z is such that the viscosity of this polysiloxane is about 2 at 25°C.
5 centipoise to about 2,500,000 centipoise), (B) a free radical-type photoinitiator, and (C) a noble metal or noble metal-containing hydrosilation catalyst. Method for producing the composition. (20) The method according to claim 19, characterized in that almost all R groups are methyl or a mixture of methyl and phenyl. (21) The method according to claim 19, wherein R^2 is vinyl. (22) x is a number such that about 1.0 to about 100 mole % of vinyl-containing siloxy units are present, and y is such that about 2.0 to about 20.0 mole % of hydrogen-containing siloxy units are present; The viscosity of the polysiloxane (A) is about 100 centipoise to about 10,000 centipoise at 25°C.
20. A method according to claim 19, characterized in that the number is centipoise. (23) The free radical type photoinitiator has the general formula: ▲mathematical formula,
There are chemical formulas, tables, etc. ▼ (wherein R^3 is a monovalent alkyl or aryl group, and Z is hydrogen, alkyl, halogen, nitro, amino or amido). The method according to item 18 or item 19. (24) the free radical type photoinitiator is selected from the group consisting of t-butyl perbenzoate, t-butyl per-p-nitrobenzoate, t-butyl per-p-methoxybenzoate, t-butyl per-p-methylbenzoate, and chlorobenzoate; 24. The method according to claim 23, characterized in that: (25) Claim 2, characterized in that the free radical type photoinitiator is t-butyl perbenzoate.
The method described in Section 4. (26) The free radical photoinitiator further has the formula:
Chemical formulas, tables, etc. are available▼Polyaromatic compound that has a chromophore (where Ph is phenyl) and at least two benzene rings that may be fused or bridged by an organic group or a hetero group 24. The method according to claim 23, comprising a sensitizer that is. (27) The method according to claim 26, wherein the photosensitizer is t-butylanthraquinone. (28) The method according to claim 18 or 19, characterized in that the noble metal or noble metal-containing hydrosilation catalyst is selected from the group consisting of platinum metal, platinum complexes, rhodium metal, and rhodium complexes. . (29) The free radical type photoinitiator is polysiloxane (
A) is present in an amount of about 0.1 to about 10 parts by weight per 100 parts by weight, and the noble metal or noble metal-containing catalyst is present in an amount of about 10 ppm to about 500 parts as precious metal based on polysiloxane (A).
20. A method according to claim 18 or 19, characterized in that the method is present in an amount of pm. (30) The method according to claim 19, further comprising mixing an organohydrogen polysiloxane. (31) The method according to claim 19, further comprising mixing a vinyl-containing polysiloxane. 32. The method of claim 19, further comprising mixing the organohydrogen polysiloxane and the vinyl-containing polysiloxane. (33) The method according to claim 19 or 32, further comprising mixing an inhibitor. (34) (A) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, almost all R is a methyl group or a mixture of methyl and phenyl groups, and R^1 is a hydrogen atom, a hydroxyl group, selected from the group consisting of methyl and methoxy groups, R^2 is a vinyl group, x is a number such that the vinyl-containing siloxy units are present in about 1.0 to about 10.0 mole percent, and y is the number of hydrogen-containing siloxy units is from about 2.0 to about 20.0 mole percent, and x+y+z is such that the viscosity of the polysiloxane is about 1 at 25°C.
(B) 0.1 to 10 parts by weight per 100 parts by weight of (A) of t-butyl perbenzoate, t-butyl perbenzoate; -p-
a free radical-type photoinitiator selected from the group consisting of nitrobenzoate, t-butyl per-p-methoxybenzoate, t-butyl per-p-methylbenzoate and chlorobenzoate, (C) 10 as platinum metal for (A); A method for producing a curable composition comprising mixing ppm to 500 ppm of a platinum metal or platinum-containing hydrosilation catalyst, (D) an organohydrogen polysiloxane, (E) a vinyl-containing polydiorganosiloxane, and (F) an inhibitor. . (35) One type of polysiloxane consisting of (a) 100 parts by weight of component A and (b) 1 to 100 parts by weight of component B, in which component A has (i) a silicon-bonded olefinic group and a silicon-bonded hydrogen atom. and (ii) a free radical type photoinitiator, wherein component B comprises a noble metal or a noble metal-containing hydrosilation catalyst dispersed in a vinyl-containing polysiloxane, and component A and component B are contained separately from each other. Manufactured products. (36) Component A(i) is a mixture of a polysiloxane having an olefinic group bonded to silicon and a polysiloxane having a hydrogen atom bonded to silicon. goods. (37) Component A(i) is a general formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, each R^ is an independently selected substituted or unsubstituted group having 1 to 20 carbon atoms is a monovalent hydrocarbon group, R^1 is hydrogen, a hydroxy group, or a substituted or unsubstituted hydrocarbon or hydrocarbon oxy group having 1 to 20 carbon atoms, and R^2 is a lower alkenyl group; , x is a number such that about 0.1 to about 20 mole percent vinyl-containing siloxy units are present, y is a number such that about 0.5 to about 50 mole percent hydrogen-containing siloxy units are present, and x+y+z The viscosity of this polysiloxane is 25℃
36. The article of claim 35, wherein the article is a polysiloxane having a polysiloxane having an average particle diameter of about 25 centipoise to about 2,500,000 centipoise. (38) I, (A) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, each R is an independently selected substituted or unsubstituted monovalent having 1 to 20 carbon atoms. is a hydrocarbon group, R^1 is hydrogen, a hydroxyl group, or a substituted or unsubstituted hydrocarbon or hydrocarbonoxy group having 1 to 20 carbon atoms, R^2 is a lower alkenyl group, and x is About 0.1 to about 20 mol% vinyl-containing siloxy units
y is a number such that the hydrogen-containing siloxy units are present in an amount of about 0.5 to 50 mole percent, and z is a number such that the viscosity of the polysiloxane is about 25 to about 2 at 25°C.
, 500,000 centipoise]
(B) a free radical-type photoinitiator, and (C) a noble metal or noble metal-containing hydrosilation catalyst; II. An article of manufacture made by applying a coating to a substrate; III. exposing the coated substrate to an ultraviolet light source to cure the coating on the substrate, and then thermally curing the coating. (39) The article according to claim 38, wherein the substrate is paper. (40) The article according to claim 38, wherein the substrate is a circuit board. (41) The article according to claim 38, wherein the article is thermally cured at room temperature. (42) The article according to claim 38, characterized in that thermosetting is performed at a high temperature. (43) I, (A) General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, each R is an independently selected substituted or unsubstituted monovalent compound having 1 to 20 carbon atoms. is a hydrocarbon group, R^1 is hydrogen, a hydroxyl group, or a substituted or unsubstituted hydrocarbon or hydrocarbonoxy group having 1 to 20 carbon atoms, R^2 is a lower alkenyl group, and x is About 0.1 to about 20 mol% vinyl-containing siloxy units
y is a number such that about 0.5 to 50 mole percent of hydrogen-containing siloxy units are present, and x+y+z is a number such that the viscosity of the polysiloxane is about 2 at 25°C.
5 to about 2,500,000 centipoise]; (B) a free radical-type photoinitiator; and (C) a noble metal or noble metal-containing hydrosilation catalyst. II. applying a coating of said curable composition to a substrate; III. exposing the coated substrate to an ultraviolet light source to cure said coating on said substrate, and then thermally curing said coating. A method of manufacturing an article comprising: (44) The method according to claim 43, wherein the substrate is paper. (45) The method according to claim 43, wherein the substrate is a circuit board. (46) The method according to claim 43, wherein the heat curing is performed at room temperature. (47) The method according to claim 43, characterized in that thermosetting is performed at a high temperature.