JPS62138845A - Photosensitive elastomer 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 Field of the Invention The present invention relates to photosensitive elastomer compositions. More specifically, the present invention relates to a photosensitive elastomer composition having excellent thermal stability and photosensitivity, which is particularly suitable for use in flexographic printing plates.

Conventional technology Conventional rubber plates for flexography and printing are produced by corroding a metal plate to produce an original plate, then manufacturing a matrix of plastics, etc., and then pouring rubber into this matrix and applying pressure. It has become popular. However, in this case, many steps are required, which is costly and time consuming, and the obtained rubber plate itself has low precision, so it has disadvantages such as requiring back-shaving before use.

In order to solve this drawback, in recent years a method has been proposed in which a flexographic printing plate is directly manufactured using a photosensitive elastomer composition.

This method eliminates the need for back-shaving, and also makes it possible to print finer designs than conventional rubber plates.

Photosensitive elastomer compositions used in flexographic printing plates generally need to be formed into sheets, and are often exposed to high temperatures during the forming process, and depending on their application, they may be stored for a long time after forming. many.

Since the photosensitive elastomer composition is often thermally insolubilized during the molding and storage process and cannot be manufactured into a product, a thermal polymerization inhibitor is usually added.

Examples of thermal polymerization inhibitors that have been proposed for this purpose include methylene blue and its derivatives, p-methoxyphenol, hydroquinone, β-naphthol,
Examples include nitrobenzene and tertiary amines.

Most of these compounds are those that suppress the radical polymerization of radically polymerizable unsaturated compounds (e.g., secondary amines, phenol derivatives, etc.) or those that suppress radical polymerization through addition reactions (e.g., It belongs to benzoquinone derivatives, etc.) and has the effect of reducing photosensitivity itself, and has no effect as a photosensitizer that improves photosensitivity.

In addition to the effect of reducing photosensitivity as described above, these known thermal polymerization inhibitors also have the effect of decreasing the thermal polymerization preventing effect when molding a photosensitive composition at high temperatures or for a long period of time, or There are drawbacks such as coloring and staining of objects, and in order to obtain a sufficient thermal polymerization prevention effect, it is necessary to use a large amount of the thermal polymerization inhibitor, but in this case, the photosensitivity of the composition There is no excuse for a significant decrease in

Incidentally, in recent years, there has been a strong demand for further shortening the plate-making time and improving plate-making efficiency, but such a decrease in photosensitivity requires a long exposure time, making it impossible to meet this demand. .

Furthermore, flexographic printing plates are sometimes required to be mounted on the plate cylinder of a printing press during printing, since colored plates are easier to align than uncolored plates. In this case, dyes, pigments, etc. are added for coloring, but the use of these causes a problem in that the photosensitive speed decreases and a long exposure time is required.

Problems to be Solved by the Invention The purpose of the present invention is to overcome the drawbacks of such conventional photosensitive elastomer compositions for flexographic printing plates, and to provide a composition having excellent thermal stability and photosensitivity. The object of the present invention is to provide a photosensitive elastomer composition suitable for use in flexographic printing plates.

Means for Solving the Problems The present inventors have conducted extensive research to achieve the above object, and as a result, have developed a photosensitive elastomer composition comprising at least one thermoplastic elastomer, an ethylenically unsaturated compound, and a photopolymerization initiator. By adding a phosphite ester to a composition, the thermal stability is significantly increased and the photosensitive speed is also significantly improved, and a thiourea derivative is further added to the composition to which a phosphite ester is added. It was discovered that by adding it, storage stability was improved in addition to the above-mentioned excellent properties, and based on this knowledge, the present invention was completed.

That is, the present invention provides (A) at least one thermoplastic elastomer, (B) an ethylenically unsaturated compound, (C)
Provides a photosensitive elastomer composition comprising a photopolymerization initiator and (D) a phosphite, and a photosensitive elastomer composition comprising this composition further containing a thiourea derivative as a component (E). It is something to do.

The thermoplastic elastomer used in the composition of the present invention has the general formula %) (A-B)n+1 or (A-B)mX (A in the formula is a heat having a glass transition temperature of 25°C or higher). a plastic non-elastomeric polymer block, B is an elastomeric polymer block having a glass transition temperature of 10° C. or less;
X is a polyfunctional residue with m bonds, n is 1 to 10,
Examples include thermoplastic elastomeric block copolymers represented by (m is 2 to 7), crystalline 1,2-polybutadiene, and acrylonitrile-butadiene copolymers having a nitrile content of 30% or more.

In the above thermoplastic block copolymer, A is polystyrene or poly(α-methylstyrene).

Examples of B are polybutadiene or polyisoprene, and X is Si or Sn.

To give further specific examples, examples of (A-B)-A include polystyrene-polybutadiene-polystyrene, polystyrene-polyisoprene-polystyrene, poly(α-
(A-B) of the above general formulas Examples include repeating the portion corresponding to up to 10 times. (B-A
)n+1B examples include polybutadiene, -polystyrene-polybutadiene, polyisoprene-polystyrene, polyisoprene-polystyrene-polyisoprene, etc., and the moiety corresponding to (B-A) in the above general formula is repeated up to 11. I can list many things. Examples of (A-B)y1+1 include polystyrene-polybutadiene-polystyrene-polybutadiene, polystyrene-polyisoprene-polystyrene-polyisoprene, poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene)-polybutadiene, and polystyrene. , polybutadiene-polystyrene-polybutadiene-polystyrene, polybutadiene, etc., and the moiety corresponding to (A-B) in the above general formula is 11
You can list things that have been repeated up to. Examples of (A-B) mX include (polystyrene-polybutadiene)4Si, (polystyrene-polyisoprene)4
si.

(Polystyrene-polybutadiene)2Sn, etc. can be mentioned.

Among these thermoplastic elastomer block copolymers, those having n of 1 in each of the above general formulas are preferred from the viewpoint of rubber elasticity and availability, such as polystyrene-polyisoprene-polystyrene, polystyrene-polybutadiene-polystyrene, polystyrene-polybutadiene-
Examples include polystyrene-polybutadiene, (polystyrene-polybutadiene)4Si, and the like.

The thermoplastic elastomeric block copolymer used in the present invention has rubber elasticity even in an unvulcanized state due to physical crosslinking of thermoplastic non-elastomeric polymer blocks sandwiching elastomeric polymer blocks, and has rubber elasticity even in an unvulcanized state. It has the characteristic of not causing any flow. However, if the molecular weight of the thermoplastic elastomeric polymer block is too small, the effect of physical crosslinking will not be achieved, and if it is too large, the rubber elasticity will be impaired. Furthermore, if the molecular weight of the elastomeric polymer block is too small, rubber elasticity cannot be achieved, and if it is too thick, the physical crosslinking effect cannot be sufficiently achieved. From this point of view,
The number average molecular weight obtained by CPC measurement using polystyrene as a standard is preferably from 2,000 to 100,000 for thermoplastic non-elastomeric polymer blocks, and from 25,000 to 1,000,000 for elastomeric polymer blocks.

Regarding the thermoplastic elastomeric block copolymer itself used in the present invention, for example, British Patent No. 13
66769.

Further, the thermoplastic elastomeric block copolymer used in the present invention can be easily obtained by the method described in US Pat. No. 3,265,765. For example, in the case of (polystyrene-polyisobrene) n-polystyrene, nibutyllithium is added to a benzene solution of styrene to obtain polystyrene anion radicals through living polymerization, and then isoprene is added to the reaction mixture and polymerized to form polystyrene. - a polyisoprene anion radical, and styrene is added to the reaction mixture again to react to obtain a polystyrene-polyisoprene-polystyrene anion radical. By sequentially adding and reacting isoprene and styrene alternately, a (polystyrene-polyisoprene)-polystyrene anion radical in which n is an arbitrary number can be obtained. The anion radical that is the active species in living polymerization is water.

It can be deactivated by adding a compound with a hydroxyl group, such as alcohol or phenol, at the end. (
A-B) other than A (B-A) n+tB or (A-B) n+
can also be easily obtained by adding and polymerizing monomers corresponding to A and B in an appropriate order. (A-B)
In the case of mX, it can be obtained by forming A-B anion radicals in the same manner as described above, and then adding 5iC14 or 5nC12.

The thermoplastic elastomeric block copolymer, crystalline 1,2-polybutadiene, and acrylonitrile-butadiene copolymer with a nitrile content of 30% or more used in the present invention have rubber elasticity in an unvulcanized state, It means something that does not exhibit fluidity at room temperature and therefore does not cause cold flow, but becomes fluid when heated.

Photosensitive elastomer composition layers for flexographic printing are normally stored for a relatively long period of time from the time the sheet is manufactured until the time it is processed into a printing plate, so if cold flow occurs during storage, thickness accuracy may be affected. becomes so bad that it becomes impossible to actually use it. Therefore, it is necessary that the basic polymer does not exhibit fluidity at room temperature, and the proportion of the polymer in the photosensitive elastomer composition must be such that it can at least maintain this property of not causing cold flow. It is necessary that there be. From this point, it is necessary that the thermoplastic elastomer be contained at least 30% by weight!
1l11 Target physical properties of the plate ((Thus, it varies, but considering rubber elasticity and ease of molding, 60 to 95
It is preferable to use it within a weight range.

From the viewpoint of rubber elasticity and plate-making properties, thermoplastic elastomeric block copolymers are preferable to crystalline 1.2-polybutadiene and acrylonitrile butadiene copolymers.

However, acrylonitrile butadiene copolymer is suitable for special applications such as those using ink with a high hydrocarbon content.

Next, the ethylenically unsaturated compounds used in the composition of the present invention include esters such as acrylic acid, methacrylic acid, fumaric acid, and maleic acid, derivatives of acrylamide and methacrylamide, allyl esters, styrene and its derivatives, and N-substituted Examples include maleimide. Specific examples include diacrylate and dimethacrylate of ethylene glycol, diethylene glycol, propylene glycol, sifropylene glycol:7-/I/, ethylene glycol, polypropylene glycol, butylene glycol, or trimethylolpropane triacrylate and trimethacrylate. , pentaerythritol tetraacrylate and tetramethacrylate, N,N'-hequinamethylene bisacrylamide and methacrylamide, diacetone acrylamide and methacrylamide, styrene, vinyltoluene, divinylbenzene, diallyl phthalate, triallyl cyanurate, fumaru Acid diethyl ester, shiftyl fumarate, dioctyl fumarate, distearyl fumarate, phtyloctyl fumarate, diphenyl fumarate, dibenzyl fumarate, shiftyl maleate, dioctyl maleate, Fumaric acid bis(3-phenylpropyl) ester, fumaric acid dilauryl ester, fumaric acid diphenyl ester, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-pentylmaleimide, N , -n-hexylmaleimide, N-cyclohexylmaleimide, N-n-
Octylmaleimide, N-2-ethylhexylmaleimide, N-nf sylmaleimide, N-laurylmaleimide, N-stearylmaleimide, N-behenylmaleimide% N-phenylmaleimide, N-chlorphenylmaleimide, N-)lyl maleimide, N-xylmaleimide compound N-penzylmaleimide), N-(6-phenylhexyl)maleimide, methylene bismaleimide, ethylene bismaleimide, trimethylene bismaleimide,
Examples include, but are not limited to, hexamethylene bismaleimide, decamethylene bismaleimide, dodecamethylene bismaleimide, phenylene bismaleimide, 2,2-siphenylenepropane bismaleimide, diphenylenemethane bismaleimide, etc. It's not something you can do.

These may be used alone or in combination of two or more.

Among these ethylenically unsaturated compounds, tefumarate and malate are superior to acrylic acid derivatives, methacrylic acid derivatives, etc. in terms of stability during the heat molding process and during storage of unexposed sheets.

Furthermore, fumarate is superior to maleate in terms of reactivity, and it is therefore preferable to use fumarate.

Further, it is preferable to use a maleimide derivative in combination because the photosensitive speed can be further increased.

The amount of the ethylenically unsaturated compound used in the composition of the present invention varies depending on the type thereof and the characteristics of the flexographic plate to be obtained, but it needs to be 1% by weight or more. If the amount of light is too small, the solvent will not be insolubilized sufficiently by light irradiation, so in the washing process with the solvent after printing the image, part of the area that should become the relief will be washed away, resulting in a satisfactory plate. I can't. On the other hand, if the amount added is too large, the plate obtained will become hard and brittle and have less rubber elasticity, so it may not be possible to use it for flexographic printing. The preferred addition amount is 5 to 30% by weight.

Examples of photopolymerization initiators useful in the photosensitive elastomer composition of the present invention include benzophenone, benzoin, pentuin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, α-methylolbenzoin, α-methylolbenzoin methyl ether. , α-methoxybenzoin methyl ether, benzoin phenyl ether, α-t-7' thylbenzoin, 2,2-dimethoxyphenylacetophenone, 2,2-jethoxyphenylacetophenone, 2
．． Examples include 2-jethoxyacetophenone, benzyl, bivaloin, anthraquinone, benzanthraquinone, 2-ethylanthraquinone, and 2-chloroanthraquinone.

Such a photopolymerization initiator is added in a polymerization effect, that is, at least 0.01% by weight. Generally 0.1-2
It is preferable to add by weight.

In the composition of the present invention, as the phosphite added for the purpose of improving photosensitivity and thermal stability, those in which an unsubstituted or substituted alkyl group or aryl group is bonded to an oxygen atom can be used.

Examples thereof include compounds represented by the general formula (R1 to R13 in the formula are each an alkyl group or an aryl group, and they may be the same or different). be able to.

Specific examples of such compounds include triphenylphosphite, tris(nonylphenyl)phosphite, triethylphosphite 1, tris(2-ethylhexyl)phosphite, tridecylphosphite, tris(tridecyl)phosphite, tris Stearyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl monotridecyl phosphite, tris(2,4-di-te)
Examples include rt-butylphenyl) phosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(tridecyl)-4,4'-isopropylidene diphenylphosphite, and tetraphenyldipropylene glycol diphosphite. Yes, but not limited to these.

Among these phosphite esters, triphenyl phosphite, diphenylmonotridecyl phosphite, and tetraphenyldipropylene glycol diphosphite are preferred from the viewpoint of thermal stability and photosensitivity improvement effect.

These phosphorous esters may be used alone or in combination of two or more, and the amount added is such that the photosensitive elastomer composition is sufficiently thermally stabilized and the photosensitivity is increased. The amount is selected to be a sufficient amount, that is, in a range of 0.01 to 10% by weight based on the composition O. If the amount added is too small, sufficient thermal stability and sensitivity improvement effects cannot be obtained; on the other hand, if it is too large, the balance of physical properties of the composition after curing will be disrupted, that is, the tensile strength will decrease, making it difficult to use as a flexographic printing plate. Becomes unfit. From the above, the preferred amount of phosphite added is 0.1 to 3
Weight range.

The photosensitive elastomer composition containing the above-mentioned thermoplastic elastomer, ethylenically unsaturated compound, photopolymerization initiator, and phosphite has significantly improved thermal stability and photosensitivity. However, if it is left in a humid place, especially in hot and humid conditions,
Separated substances may be generated, which may lead to a deterioration in product quality, such as a decrease in sensitivity, thermal stability, physical properties, and resolution of the printing plate, and a loss of appearance.

Therefore, in the present invention, a thiourea derivative may be further added to the composition in order to suppress the generation of separated substances over time.

This thiourea derivative has the general formula (in the formula, R11 and R'12 are each a hydrogen atom,
Examples include compounds represented by an alkyl group or an alkyl group (which may be the same or different).

- Specific examples of such compounds include trimethylthiourea, N,N'-diethylthiourea, N,N'-diptylthiourea, tributylthiourea, tetrabutylthiourea, N,N'-dilaurylthiourea, N, , N'-diphenylthiourea, 1,3-bis(dimethylaminopropyl)-2-thiourea, ethylenethiourea, etc., but are not limited to these.

Among these thiourea derivatives, alkylated thiourea has a greater effect of suppressing the generation of separated substances than arylated thiourea. However, in such cases, alkylated thiourea is preferable than arylated thiourea because the scorch tendency of the composition is smaller when using alkylated thiourea. In this case, thiourea having a small number of carbon atoms is advantageous in terms of price, and furthermore, the smaller the number of substituents bonded to the N-position of thiourea, the greater the effect of suppressing the generation of separated substances. becomes thick, so the number of substituents is preferably 2 or 3. Considering these points, N, N
'-Dibutylthiourea and tributylthiourea are preferred.

These thiourea derivatives may be used alone or in combination of two or more, and the amount added is a sufficient amount to suppress the generation of separated substances in the photosensitive elastomer composition, that is, the composition 0.1-3 for objects
Select from the weight range.

If the amount added is too small, a sufficient effect of suppressing the generation of separated substances will not be obtained, and if it is too large, problems such as a decrease in the tensile strength of the composition after curing and coloring of the composition will occur. From the above, the preferred amount of the thiourea derivative to be added is in the range of 0.2 to 1% by weight.

The photosensitive elastomer composition of the present invention may contain 0.001 to 2% by weight of a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include 2,6-di-t-bunaru-p-cresol, p-methoxyphenol, and pentaerythritol tetrakis (3-(3').

5'-di-t-butyl-4'-hydroxy)phenylpropionate], hydroquinone, t-butylcatechol, t-butylhydroxyaninol, 4°4'-butylidenebis(3-methyl-6-t-butyl) ) phenol, etc.

In the composition of the present invention, by using these thermal polymerization inhibitors and the phosphite ester in combination, an excellent effect of improving thermal stability can be obtained.

Furthermore, the photosensitive elastomer composition of the present invention may contain a plasticizer if desired. This plasticizer accelerates the removal of the unexposed portion of the photosensitive elastomer composition, improves the physical properties of the cured portion, and further assists in the production of the photosensitive elastomer composition layer, especially in molding, and achieves the goals. A range of 2 to 40 parts by weight is added depending on the properties to be added. These include hydrocarbon oils such as naphthenic oil and paraffin oil, low molecular weight polystyrene (molecular weight 300
(below), α-methylstyrene-vinyltoluene copolymer, petroleum resin, pentaerythritol ester of hydrogenated rosin, polyterpene resin, polyester resin, polyethylene, poly(α-methylstyrene), polyacrylate, liquid 1, Examples include 2- and 1,4-polybutadiene, liquid acrylonitrile butadiene copolymer, liquid sterentadiene copolymer, stearic acid, polypentadiene, polyurethane, ethylene propylene diene rubber, and the like.

Since the photosensitive elastomer composition of the present invention exhibits tackiness depending on its composition, the purpose is to improve contact with a transparent image carrier to be stacked thereon.

And to enable reuse of the transparent image carrier, its surface can be provided with a laminate layer of a thin film of polyethylene, polypropylene, polyester, polystyrene, etc. The film is stripped off after exposure through the overlying transparent image carrier. For similar purposes, the film gage may be provided with a thin, solvent-soluble, flexible layer. in this case,
When the unexposed area is eluted after exposure through the transparent image carrier, that layer is simultaneously removed by dissolution or the like.

The photosensitive elastomer composition of the present invention (which can be prepared by various methods, for example, chloroform, carbon tetrachloride, 1,1,1-4-lichloroethane, tetrachlorethylene, trichlorethylene, methyl ethyl ketone, methyl isobutyl The photosensitive elastomer composition can be mixed with a suitable solvent such as ketone, toluene, tetrahydrofuran, etc. and cast into a mold to evaporate the solvent to form a plate as it is, or the photosensitive elastomer composition can be heated to form a plate. If you press, you will be able to get a layer with good precision.
Alternatively, they can be mixed in a roll mill without the use of a solvent, and then formed into a sheet of desired thickness by extrusion, injection, pressing, calendering, etc.

The protective film and support film can be brought into close contact with the photosensitive layer by roll lamination after forming the sheet. A more precise photosensitive layer can be obtained by hot pressing after lamination.

If a thin flexible layer, such as a layer of crystalline 1,2-polybutadiene, soluble polyamide, or partially saponified polyvinyl acetate, is to be provided on the surface of the photosensitive layer, it can be dissolved in a suitable solvent and then removed. The solution may be directly coated on the surface of the photosensitive layer, or it may be coated once on a film of polyester, polypropylene, etc., and then the entire film may be laminated onto the photosensitive layer and transferred.

Actinic light sources used to insolubilize the photosensitive elastomer composition of the present invention include low-pressure mercury lamps, high-pressure mercury lamps, ultraviolet fluorescent lamps, carbon arc lamps, xenon lamps, zirconium lamps, sunlight, and the like.

After the photosensitive elastomer composition of the present invention is irradiated with light through a transparent image carrier to form an image, the solvent used for eluting the unexposed areas should be used to thoroughly solvent the unexposed areas and to form an image after exposure. It is necessary that the material has almost no effect on the image area, for example, 1,1.1-)lychloroethane, tetrachlorethylene, trichlorethylene,
These include tetrachloroethane, toluene, etc., and alcohols of 60% by weight or less, such as ethanol, impropatol, n-butanol, etc., mixed therewith. The unexposed areas are eluted by spraying from a nozzle or by brushing with a brush.

Effects of the Invention The photosensitive elastomer composition of the present invention contains a thermoplastic elastomer, an ethylenically unsaturated compound, a photopolymerization initiator, and a phosphite, or contains these components and a thiourea derivative. In addition to being excellent in thermal stability, the latter composition also has excellent photosensitivity, and in addition to these excellent properties, it also has excellent storage stability. .

Therefore, the photosensitive elastomer composition of the present invention is particularly suitable for use in flexographic printing plates, and can also be used for photoresists and screen printing screens.

Example Next, the present invention will be explained in more detail by way of examples.

The photosensitivity, thermal stability and degree of difficulty in generating separation of the photosensitive elastomer composition were determined as follows.

(1) Cut a sheet of the photosensitive composition into a size of 3×6c1n,
On top of that, two black rubber plates of 6×3 Iyn are arranged so as to cover each rod of the sheet.

This is placed under light using an ultraviolet fluorescent lamp with an intensity of 0.80 mW/7, and 20 minutes after removing one black rubber plate, the sheet is removed from under the light source.

Next, the polyester film on the side opposite to the side irradiated with light was peeled off, and elution was performed using a brush with a mixture of tetrachloroethylene/n-butanol (μ) until the unexposed area was completely washed out. After drying and warming at 60°C for 1 hour, cool to room temperature. In this way, the thickness of the cured composition is measured by exposure for 26 minutes.

(2) Thermal stability Plastudor PLV151 type manufactured by Prabender Co., Ltd.
Using a device equipped with a roller mixer model W50EC, the composition 402 was charged into a part of the mixer and heated to 200°C.
, 150 rpm, and determine the torque increase start time by examining the change in torque over time.

(3) Difficulty in generating separated substances Cut a sheet □ of the composition into a size of 4 x 4 crIM, and place it in a constant temperature and humidity chamber at 50°C and 804 (relative humidity) until n1 separated substances are generated. Find out the number of days.

Example 1 Solution polymerized styrene-butadiene rubber [manufactured by Asahi Kasei Kogyo ■,
Product name: Tsurpuren 12051250? , Liquid Polybutadiene [Nippon Petrochemical Corporation, trade name B-20001130
f, di-n-octyl fumarate 30f, N-laurylmaleimide 8F, 2,2-dimethoxyphenylacetophenone 8? , 0.82 of 2,6-di-tert-butyl-p-cresol were kneaded in a Nigu.

The thus prepared composition was sandwiched between 100 μm polyester films, placed inside a spacer with a thickness of 3 mm, and pressed at 140° C. to obtain a sheet of the photosensitive elastomer composition.

The photosensitivity of the sheet of the composition thus obtained and the thermal stability of the composition were determined.

Further, in the above method, a composition was prepared with the same formulation as above except that phosphite ester 42 was included, and then a sheet of the composition was prepared in the same manner, and the photosensitivity and thermal stability were determined. These results are shown in Table 1.

Table 1 Example 2 Styrene-isoprene-styrene block copolymer [
Manufactured by Shell Chemical Co., Ltd., trade name Cauliflex TR1107]
'250 r, liquid polybutadiene [manufactured by Japan Agency ■, trade name B-3000] 120? , 1,6-hexanethiol dimethacrylate 12F, 2,2-dimethoxyphenylacetophenone 89,2,6-ditert
-Butyl-p-cresol 0.82 was kneaded in a kneader to obtain a photosensitive elastomer composition, and then formed into a sheet in the same manner as in Example 1. A sheet of the composition was prepared, and the photosensitivity and thermal stability were I asked for it.

In addition, in the above method, a composition was prepared with the same formulation as above except that it contained sulfurous acid entel 42, and then a sheet of the composition was prepared in the same manner, and the photosensitivity and thermal stability were determined. . These results are shown in Table 2.

Table 2 Example 3 Styrenic thermoplastic elastomer [manufactured by Asahi Kasei Corporation ■, trade name Toughpre/A] 2509 b Liquid polybutadiene [manufactured by Nippon Oil ■, trade name B-3000] 130? ,
Di-n-octyl fumarate 30r, 2,2-dimethoxyphenylacetopheno 785', 2,6-tert
-butyl-p-cresol 0.82 was kneaded in a kneader to obtain a photosensitive elastomer composition, and then formed into a sheet in the same manner as in Example 1 to prepare a sheet of the composition. Thermal stability was determined.

Further, in the above method, compositions were prepared in the same manner except that various amounts of diphenylmonotridecyl phosphite were used in place of 2,6-di-tert-butyl-p-cresol, and then the compositions were A sheet was prepared and its photosensitivity and thermal stability were determined.

These results are shown in Table 3.

Table 3 Experiment 2"6.-Gtert')7x=hゝノ Cured thickness Torque valve opening-Phthyl-p-tridecylphos number Cresol (2) Phi), (y)
('') Start time (minutes) 11 0.8
1.1
912-2
1.3 2113 -
8 1.5
5914-20 2.0
As can be seen from the results of Examples 1 to 3, the compositions containing phosphite exhibit excellent photosensitivity and thermal stability.

Example 4 Styrenic thermoplastic elastomer [manufactured by Asahi Kasei Corporation, trade name: Tuffrene A] 25 (1, liquid polybutadiene [manufactured by Nippon Petrochemical Corporation, trade name: B-20001110?, tetraethylene glycol dimethacrylate] 12f, N - Lauryl maleimide 82, benzo, ethyl ether 8
F, 2.6-di-tert-butyl-p-cresol 0.82 and various phosphites 8? A photosensitive elastomer composition was prepared by kneading or kneading these and various types of tributylthiourea in a kneader, and then a sheet of the composition was prepared in the same manner as in Example 1.

The degree of difficulty in generating separation and photosensitivity of the sheet of the composition thus obtained was determined, and the thermal stability of the composition was determined. The results are shown in Table 4.

Example 5 Styrene-isoprene-styrene block copolymer [
Manufactured by Shell Chemical Co., Ltd., trade name Cauliflex TR1107]
300, process oil [manufactured by Idemitsu Kosan, product name A]
C-460]45, di-n-octyl fumarate 6F,
2.2-dimethoxyphenylacetophenone 62.2.
6-tert-butyl-p-cresol 0.3 y
A photosensitive elastomer composition was prepared by kneading and hiscyphenyl monodecyl phosphite 62, or various thiourea derivatives 32 with a kneader, and then a sheet of the composition was prepared in the same manner as in Example 1. , the degree of difficulty in generating separation, photosensitivity, and thermal stability were determined. The results are shown in Table 5.

Example 6 Styrenic thermoplastic elastomer [manufactured by Asahi Kasei Kogyo ■, trade name: Tuffrene A] 814. Styrene-based special transparent paper resin [
Manufactured by Asahi Kasei Corporation, product name Asaflex 810127
? , solution polymerized styrene-butadiene rubber [Asahi Kasei Corporation■
Manufactured by Tsurprene 12051200? , liquid polybutadiene [manufactured by Nippon Petrochemical Co., Ltd., trade name B-3000]
48? , di-n-butyl fumarate 12F, 2.2-
Dimethoxyphenylacetophenone 92.2,6-di-tert-butyl-p-cresol 0.42 and diphenylmonotridecyl phosphite 82, or these and various amounts of tributylthiourea are kneaded in a kneader to make a photosensitive elastomer. A composition was prepared, and then a sheet of the composition was prepared in the same manner as in Example 1, and the degree of difficulty in generating separation substances, photosensitivity, and thermal stability were determined. The results are shown in Table 6.

Example 4. Crystalline 1,2-polybutadiene [manufactured by Japan Synthetic Rubber ■,
Product name PB 810] 250? , liquid polybutadiene [manufactured by Nippon Petrochemical Co., Ltd., trade name B-2000] 12
59.

Di-n-octyl maleate 302, benzoin isobutyl ether 4r, P-methoxyphenol 0.27
A photosensitive elastomer composition was prepared by kneading and diphenyl monotridecyl phosphite 47 or 82, or these and tributylthiourea 12 in a kneader, and then a sheet of the composition was prepared in the same manner as in Example 1. Then, the degree of difficulty in generating separated substances, photosensitivity, and thermal stability were determined. The results are shown in Table 7.

From Table 7 and above, and from the results of Examples 4 to 7, by adding a thiourea derivative to a composition containing a phosphite ester,
It can be seen that the generation of separated substances over time can be suppressed without reducing photosensitivity and thermal stability.

Procedural amendment March 2, 1988 Patent Application No. 277903 2, Name of the invention Photosensitive elastomer composition 3, Person making the amendment Relationship to the case Patent applicant 1-chome Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture No. 2-6 (003) Asahi Kasei Industries Co., Ltd. Representative Masaomi Seko 11 Agent Kawa Shimitsu Kuninobu Building 8th Floor 1-5, 2-2-2 Shinbashi, Minato-ku, Tokyo 15, Date of amended order Voluntary 6. Number of inventions increased by amendment 0 7, subject of amendment Detailed explanation of invention in specification column 8,
Contents of the amendment (1) "Bras Tudor" in the 4th line from the bottom of Beno No. 33 of the specification will be corrected to "Plasti Two Goo."

(2) Table 4 on page 40 of the same document is corrected as shown in the attached sheet.

,'' ・＼ /' (3) 9 corrections are made to Table 5 on page f542 as shown in the attached sheet.

/'/'/' (4) Table 6 of the 44th Beno has nine corrections as shown in the attached sheet.

/'//' (5) On page 45, line 1, "Example 4" is corrected to "Example 7."

(6) On page 45, line 3 [Product name PB810J]
[Product name will be corrected to RB810J.

(7) Table 7 on page 46 will be corrected as shown in the attached sheet.

vg T table

Claims (1)

[Claims] 1 (A) at least one thermoplastic elastomer, (B
) ethylenically unsaturated compound, (C) photopolymerization initiator and (
D) A photosensitive elastomer composition containing a phosphite. 2 The thermoplastic elastomer has the general formula (A-B)_n-A (B-A)_n_+_1-B or (A-B)_mX (A in the formula is a thermoplastic non-elastomer having a glass transition temperature of 25°C or higher). B is an elastomeric polymer block having a glass transition temperature of 10°C or less;
X is a polyfunctional residue with m bonds, n is 1 to 10,
The composition according to claim 1, which is at least one thermoplastic elastomeric block copolymer represented by: 3 Phosphite ester has general formula ▲ mathematical formula, chemical formula, table, etc. ▼, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 to R_1_3 are each an alkyl group or an aryl group, and they are the same and The composition according to claim 1 or 2, which is at least one compound selected from the compounds represented by (which may be different from each other). 4 (A) at least one thermoplastic elastomer, (
B) ethylenically unsaturated compound, (C) photoinitiator, (
A photosensitive elastomer composition comprising D) a phosphite and (E) a thiourea derivative. 5 The thermoplastic elastomer has the general formula (A-B)_n-A (B-A)_n_+_1-B (A-B)_n_+_1 or (A-B)_mX (A in the formula has a glass transition temperature of 25°C or higher). B is a thermoplastic non-elastomeric polymer block having a glass transition temperature of 10° C. or less;
X is a polyfunctional residue with m bonds, n is 1 to 10,
5. The composition according to claim 4, which is at least one thermoplastic elastomeric block copolymer represented by: (m is 2 to 7). 6 Phosphite ester has a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ Numerical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 to R_1_3 are each an alkyl group or an aryl group, and they are the same and The composition according to claim 4 or 5, which is at least one compound selected from the compounds represented by (which may be different from each other). 7 Thiourea derivatives have general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. 6. The composition according to claim 4, 5 or 6, which is at least one compound selected from the following compounds (which may be different from each other).