JP2989388B2 - Polymerizable rubber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerizable rubber suitable as a raw material for paints, UV inks, flexographic materials, photoresists, adhesives and coatings.

[0002]

2. Description of the Related Art A polymerizable rubber having a polymerizable carbon-carbon double bond at a terminal is known. In particular, a urethane group-containing reaction product obtained by reacting a diene-based liquid rubber having a hydroxyl group, an ethylenically unsaturated monomer having a hydroxyl group, and a diisocyanate compound has excellent physical properties. Also,
Techniques for increasing the photocurability by adding a photopolymerization initiator to this reaction product (polymerizable rubber) and for preventing gelation during storage by adding a thermal polymerization inhibitor are known. (JP-A-56-86903).

[0003]

However, when a composition is produced by mixing the above-mentioned polymerizable rubber as a main component, a polymerization initiator and the like, and the composition is cured, the flexibility is low. It has been found that the method cannot be applied to the use applied to the surface of a certain base material. Where the present inventors have pursued this cause, it is difficult for the polar group having an adsorption effect to the base material to be present in the chemical structure of the polymerizable rubber, and the volume shrinkage when the composition is cured is not easily reduced. This was caused by remaining as internal stress in the cured product, causing a decrease in adhesive strength. When the above composition is produced, it is common to add a low molecular weight polymerizable monomer such as 2-ethylhexyl acrylate. However, the above-mentioned conventional urethane group-containing polymerizable rubber has low compatibility with various polymerization reactive monomers. For this reason, it was very difficult to handle, especially when preparing photocurable inks, paints and adhesives.

[0004] It is an object of the present invention to provide a polymerizable rubber having particularly high adhesive strength to a flexible substrate and having high compatibility with various low molecular weight polymerization reactive monomers.

[0005]

According to the present invention, there is provided the following formula (I):
The present invention relates to a polymerizable rubber having a structural formula represented by the following formula:

Embedded image [R ¹ represents a hydrogen atom or a methyl group. R ² represents a residue obtained by removing two isocyanate groups from a diisocyanate compound. R ³ represents a residue obtained by removing two hydroxyl groups from a dihydric alcohol having a molecular weight of 500 or less. R ⁴ represents a hydrocarbon group having 2 to 12 carbon atoms or a polyoxyalkylene group having 2 to 12 carbon atoms. l shows the integer of 1-5. m
Represents an integer of 1 or more. n shows the integer of 1-16.
x represents an integer of 1 or more. A represents 10 repeating units
The above is a diene-based liquid rubber of 1000 or more, and (m +
and x) a residue obtained by removing m hydroxyl groups from a diene-based liquid rubber having hydroxyl groups. ]

[0006]

The present inventors have studied various chemical structures in order to solve the above problems. In the process, a hard segment having a urethane bond composed of a dihydric alcohol and a diisocyanate compound and a soft segment composed of a diene liquid rubber are introduced into a skeleton, and at the same time, a hydroxyl group is introduced into a molecule. The present inventors have found that surprisingly high performance, which has never been seen before, can be obtained in terms of toughness and flexibility of a cured product, adhesion to a substrate, and water developability.

That is, it has been discovered that by introducing a highly polar hydroxyl group and a polyurethane segment into a polymerizable rubber molecule, the adhesive force to a substrate is increased, and the compatibility with various polymerizable monomers is remarkably improved. In addition, a cured product obtained by mixing the above polymerizable rubber with a polymerizable monomer or the like and hardening has both high toughness and flexibility. Furthermore, the photopolymerizable rubber of the present invention has a high affinity for water and can be used very suitably as a raw material for water development.

[0008]

Hereinafter, the present invention will be described more specifically. The polymerizable rubber of the present invention is obtained by reacting the following components.

[0009]

Table 1 Diene-based liquid rubber having (m + x) hydroxyl groups Ethylenically unsaturated monomer having one hydroxyl group Diisocyanate compound Dihydric alcohol having a molecular weight of 500 or less

The diene-based liquid rubber can be represented by the following structural formula. A (OH) _{m + X.} Examples of this diene-based liquid rubber are so-called star polymer-based or branched polymer-based synthetic rubbers. Specific examples include polymers having a number average molecular weight of about 1,000 to 50,000 among butadiene rubber, hydrogenated butadiene rubber, isoprene rubber, hydrogenated isoprene rubber, chloroprene rubber, and the like. A total of (m + x) hydroxyl groups are bonded to an arbitrary position in the skeleton of the rubber molecule, and the number thereof is 0.1 on average.
It is produced as a mixture of synthetic rubbers having about 5 to 6 or different numbers of hydroxyl groups. Therefore, even if (m + n) of the raw synthetic rubber is 1 or less, a mixture containing two or more can be used. A hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferably bonded at positions other than the bonding position of the hydroxyl group. Two or more diene liquid rubbers may be mixed.

The ethylenically unsaturated monomer having one hydroxyl group has the following structural formula.

Embedded image

R ¹ represents a hydrogen atom or a methyl group. R
⁴ represents a hydrocarbon group having 2 to 12 carbon atoms or a polyoxyalkylene group having 2 to 12 carbon atoms. l shows the integer of 1-5. In this ethylenically unsaturated monomer, a terminal hydroxyl group reacts with a diisocyanate compound described later.

Representative examples of the ethylenically unsaturated monomers include 2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Hexapropylene glycol monoacrylate, polypropylene glycol monomethacrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, trimethylolpropanedi ( Meth) acrylates,
Glycidol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaeristol penta (meth) acrylate, glycerol di (meth)
Acrylate and the like. These can be used alone or as a mixture.

The above "diisocyanate compound" is represented by the following structural formula. R ² (NCO) ₂ Specific examples of the diisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate _, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, p-phenylene diisocyanate, bis (isocyanate methyl isocyanate). ) Cyclohexane, dicyclohexylmethane diisocyanate, lysine diisocyanate and the like. These can be used alone or in combination.

Dihydric alcohol R ³ (OH) ₂ having a molecular weight of 500 or less
Are the case where a cyclic structure is contained in the R ³ portion;
The R ³ moiety may be an acyclic aliphatic group. Specific examples of the dihydric alcohol having a cyclic structure include cyclohexane-1.4-diol, cyclohexane-1.4-dimethanol, bisphenol A, bisphenol F, bisphenol S, 1.4-hydroquinone, benzene-1. Four
-Dimethanol and the like.

R ³ (OH) ₂ is preferably represented by the following structural formula.

Embedded image Here, R ⁵ has 2 to 20 carbon atoms (preferably 2 to 12 carbon atoms).
) Of the compound residues. R ⁵ has 2 to 8 carbon atoms
Alkylene or polyoxyalkylene groups are particularly preferred. R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a (meth) acryloyloxy group, a (meth) acryloyloxymethyl group, an allyloxy or allyloxymethyl group.

In the above structural formula, R ⁵ has 2 to 2 carbon atoms.
Specific examples of the alkyl group or polyoxyalkylene group of 8 include ethylene glycol, diethylene glycol, triethylene glycol, 1.2-propylene glycol, 1.3-propylene glycol, 1.3-butanediol, and 1.4- Butanediol, 1.5-pentanediol, 1.6-hexanediol and the like. When R ⁶ or R ⁷ is an acryloyloxy group, a methacryloyl group, or an allyloxy group, the dihydric alcohol itself has radical polymerizability. Specific examples include trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, and glycerol α-monoallyl ether.

Of the above structural formulas, those further represented by the following structural formulas are preferred.

Embedded image Here, R ⁸ and R ⁹ are each independently or one of
An alkyl group having 1 to 12 carbon atoms, a (meth) acryloyloxymethyl group having 1 to 12 carbon atoms, a (meth) acryloyloxy group having 1 to 12 carbon atoms, an allyloxy group having 1 to 12 carbon atoms or allyl It is an oxymethyl group.

When a dihydric alcohol having such a structure is used, a hydroxyl group is bonded to two primary carbons, and
The carbon sandwiched between two primary carbons is replaced by R ⁸ and R ⁹ . For this reason, a moderate steric hindrance is given to the urethane reaction of each hydroxyl group, and the reactivity of the dihydric alcohol is moderate. If it has a secondary alcohol or tertiary alcohol structure, the urethane reaction rate is low and it is not suitable for mass production. If R ⁸ and R ⁹ are hydrogen atoms, on the contrary, the urethane reaction rate becomes too fast and the control becomes difficult, so that it is not suitable for mass production. In addition, the presence of the alkylyl groups R ⁸ and R ⁹ suppresses crystallization of the polyurethane portion of the present invention, increases solubility in various solvents and monomers, and facilitates use as a copolymer component. Such dihydric alcohols include neopentyl glycol, 2
-Ethyl-2-methylpropanediol, 2-methylpropanediol, 2-ethyl-hexane-1,6-diol, pentaerythritol di (meth) acrylate, and the like. The “dihydric alcohol having a molecular weight of 500 or less” may be used alone or as a mixture of two or more.

The reaction molar ratio of each of the above raw materials will be described.
You. Diene-based liquid rubber A (OH)_{m + X}React 1 mole of
In the case, "dihydric alcohol having a molecular weight of 500 or less" R^Three(OH)_TwoIs
mn mole is required. Diisocyanate compound R^Two(NCO)
_TwoRequires (mn + m) moles. Ethylenically unsaturated single
The monomer reacts in mmol.

In the polymerizable rubber of the present invention, the molecular chain of the diene liquid rubber constitutes a soft segment. The following repeating units of a urethane bond between R ² and R ³ constitute a hard segment.

Embedded image The value of n indicates the length of the hard segment. The molecular chain of the diene-based liquid rubber has low polarity and low cohesiveness. The above-mentioned hard segment is constituted by repeating polar and highly cohesive urethane bonds, whereby micro-phase separation occurs between the soft segment and the hard segment. When crosslinks are formed between polymerizable ethylenically unsaturated groups provided at the ends of the hard segments, a large number of hard segments are firmly bonded to each other. Therefore, when a cured product is formed by polymerizing the polymerizable rubber of the present invention, a cured product having high strength and high elongation can be obtained.

The molecular weight of the above dihydric alcohol R ³ (OH) ₂ is
If it exceeds 500, the above-described phase separation between the hard segment and the soft segment hardly occurs, and desired characteristics cannot be obtained.

N is the number of repeating units of a urethane bond comprising a diisocyanate compound and a dihydric alcohol. When n is 17 or more, rubber-like properties are lost, which is not preferable. If n is 0, the effect of the present invention cannot be obtained because the above hard segment does not exist.

The value of m is 1 to 6. When m is 7 or more, the cured product after the polymerization reaction becomes too hard, its elasticity is reduced, and the desired rubber elasticity cannot be obtained. x is an integer of 1 or more. When there is no hydroxyl group in the polymerizable rubber, that is, when x = 0, the adhesion of the cured product to a base material such as plastic or metal becomes weak, and the compatibility with water becomes poor, so that the Cannot be used as a raw material. According to the present invention, when a hydroxyl group is provided in the polymerizable rubber, the adhesion of the cured product is improved by the effect of adsorbing the base material. In addition, compatibility with various polymerizable monomers as a diluent component in the polymerizable composition is improved, and the range of application is expanded. In addition, the compatibility with water is improved, and it can be used as a raw material for water development.

An example of the process for producing the polymerizable rubber of the present invention will be described. In a suitably selected solvent, the diisocyanate compound R ² (OH) ₂ is added little by little to the R ³ (OH) ₂ (mn) mole in the ratio of (mn + m) mole, and the reaction is carried out. Is obtained. In this reaction, a catalyst such as dibutyltin dilaurate, tin octylate, triethylamine, and triethyldiamine is used. The reaction temperature is
It should be between 10 and 120 ° C, preferably between 40 and 80 ° C. Next, to this compound, one mole of an ethylenically unsaturated monomer having one hydroxyl group is gradually added and reacted to obtain a compound having an isocyanate group at one terminal. Next, 1 mol of diene liquid rubber A (OH) _{m + x} is gradually added.

At the time of this synthesis reaction, a thermal polymerization inhibitor is added as necessary to suppress the thermal polymerization reaction. Hydroquinone, t-butylcatechol, O
-Nitrophenol, m-nitrophenol, p-nitrophenol, 2.4-dinitrophenol, 2,4,6-
Trinitrophenol, p-methoxyphenol, p-
Benzoquinone, phenothiazine, anthraquinone, 2, 6
-Di-t-butylhydroxytoluene and the like. These may be used alone or as a mixture. The weight ratio of the thermal polymerization inhibitor is 0.05-1% by weight of the total blend weight.

After the completion of the above synthesis reaction, the solution after the completion of the reaction is heated under vacuum to remove the solvent, and the polymerizable rubber is taken out as a single substance. Or, a monomer having good compatibility with the polymerizable rubber and having a higher boiling point than the solvent is added,
The solvent is gradually removed by heating under vacuum, and the monomer solution of the polymerizable rubber is taken out. The polymerizable rubber of the present invention can be polymerized alone or with other polymerizable monomers. Examples of the polymerization initiator that can be used in this case include benzoyl peroxide, lauroyl peroxide, tertiary butyl peroxide, or an oxidized ring polymerization initiator comprising a combination of these peroxides and amines, azobisisobutyronitrile. And a thermal polymerization initiator such as azobisvaleronitrile, benzophenone and the like.

Hereinafter, more specific experimental results will be described. First, a polymerizable rubber was manufactured according to the following synthesis examples. Example 1 A 1-liter reaction vessel was provided with a stirrer, a temperature controller, a thermometer, and a condenser. In this reaction vessel, 2,4-tolylene diisocyanate R ² (NCO) ₂ : 57.9
g and neopentyl glycol R ³ (OH) ₂ (molecular weight 104): 3
1.9 g were dissolved in 170 g of dioxane. The temperature of this solution was maintained at 50 to 60 ° C., and the reaction was performed under a nitrogen atmosphere for 3 hours.
Then, 2-hydroxyethyl acrylate CH ₂ CHCH—CO
OCH ₂ CH ₂ OH: 3.0 g, dibutyltin dilaurate as a urethanization catalyst: 0.15 g, polymerization inhibitor (p-methoxyphenol): 0.15 g, and dioxane 50 g were added, and the mixture was heated at 50 to 60 ° C. under a nitrogen atmosphere. The reaction was performed for 2 hours.

Next, liquid isoprene "LIR-506"
294 g (manufactured by Kuraray Co., Ltd.) was dissolved in 380 g of dioxane, and this solution was further added to the above reaction solution, and reacted at 50 to 60 ° C. for 5 hours under a nitrogen atmosphere. From the infrared absorption spectrum, it was confirmed that the absorption of the isocyanate group (2250 cm ^-1 ) had disappeared, and the reaction was terminated. Then, vacuum dryer
(Yamato Scientific Co., Ltd .: DP-22 type) to remove dioxane to obtain a solid polymer. When measured by infrared absorption spectrum, characteristic absorption was observed at 3,300, 2920, 1710, and 1640 cm ^-1 . The structural formula of this polymerizable rubber is shown.

[0030]

Embedded image

Example 2 A 1-liter reaction vessel was equipped with a stirrer, a temperature controller, a thermometer, and a condenser. In this reaction vessel, isophorone diisocyanate R ² (NCO)
₂ : 53.4 g and hexamethylenediol R ³ (OH) ₂ (molecular weight
118): 25.1 g was dissolved in 150 g of dioxane. The temperature of this solution was maintained at 50 to 60 ° C., and the reaction was performed under a nitrogen atmosphere for 3 hours. Then, 2 hydroxyethyl methacrylate
CH ₂ CC (CH ₃ ) —COOCH ₂ CH ₂ OH: 5.2 g, triethylenediamine 0.15 g, polymerization inhibitor hydroquinone: 0.15 g,
And 50 g of dioxane, and reacted at 50-60 ° C. for 2 hours under a nitrogen atmosphere.

Next, the liquid isoprene "LIR-506"
306 g (manufactured by Kuraray Co., Ltd.) was dissolved in 400 g of dioxane, and this solution was further added to the above reaction solution, and reacted at 50 to 60 ° C. for 5 hours under a nitrogen atmosphere. From the infrared absorption spectrum, it was confirmed that the absorption of the isocyanate group (2250 cm ^-1 ) had disappeared, and the reaction was terminated. Next, dioxane was removed with a vacuum dryer to obtain a solid polymer. 3300, 2920, 1710, 1640
Characteristic absorption was observed at cm ⁻¹ . The structural formula of this polymerizable rubber is shown.

[0033]

Embedded image

Example 3 A 1-liter reaction vessel was provided with a stirrer, a temperature controller, a thermometer, and a condenser. In this reaction vessel, 2,4-tolylene diisocyanate R
² (NCO) ₂ : 16.6 g and 1.4-butanediol R ³ (OH) ₂ (molecular weight 90): 5.7 g were dissolved in 80 g of dioxane. The temperature of this solution was maintained at 50 to 60 ° C., and the reaction was performed under a nitrogen atmosphere for 3 hours. Then 2-hydroxyethyl acrylate: 9.
2 g, 0.15 g of dibutyltin dilaurate, 0.15 g of p-methoxyphenol and 50 g of dioxane were added, and the mixture was reacted at 50 to 60 ° C. for 2 hours under a nitrogen atmosphere.

Next, liquid isoprene "LIR-506"
365 g (manufactured by Kuraray Co., Ltd.) was dissolved in 470 g of dioxane, and this solution was further added to the above reaction solution, and reacted at 50 to 60 ° C. for 5 hours under a nitrogen atmosphere. From the infrared absorption spectrum, it was confirmed that the absorption of the isocyanate group (2250 cm ^-1 ) had disappeared, and the reaction was terminated. Next, dioxane was removed with a vacuum dryer to obtain a solid polymer. 3300, 2920, 1710, 1640
Characteristic absorption was observed at cm ⁻¹ . The structural formula of this polymerizable rubber is shown.

[0036]

Embedded image

Example 4 In the 1 liter reactor described in Example 1, 90.4 g of 4,4'-diphenylmethane diisocyanate R ² (NCO) _{2 and} 1.4-butanediol R
³ (OH) ₂ : 30.5 g was dissolved in 210 g of dioxane. The temperature of this solution was maintained at 50 to 60 ° C., and the reaction was performed under a nitrogen atmosphere for 3 hours. Then 2-hydroxyethyl methacrylate:
2.9 g, 0.15 g of dibutyltin dilaurate, 0.15 g of hydroquinone and 50 g of dioxane were added, and reacted at 50-60 ° C. for 2 hours under a nitrogen atmosphere.

Next, liquid isoprene "LIR-503"
259 g (manufactured by Kuraray Co., Ltd.) was dissolved in 340 g of dioxane, and this solution was further added to the above reaction solution, and reacted at 50 to 60 ° C. for 5 hours under a nitrogen atmosphere. From the infrared absorption spectrum, it was confirmed that the absorption of the isocyanate group (2250 cm ^-1 ) had disappeared, and the reaction was terminated. Next, dioxane was removed with a vacuum dryer to obtain a solid polymer. 3300, 2920, 1710, 1640
Characteristic absorption was observed at cm ⁻¹ . The structural formula of this polymerizable rubber is shown.

[0039]

Embedded image

Example 5 In the 1 liter reactor described in Example 1, isophorone diisocyanate R ² (NCO) ₂ : 1
01.2 g and neopentyl glycol R ³ (OH) ₂ : 34.5 g
Was dissolved in 250 g of dioxane. Raise the temperature of this solution to 50
The mixture was kept at 6060 ° C. and reacted under a nitrogen atmosphere for 3 hours. Then, 2hydroxyethyl acrylate: 17.5 g, triethylenediamine: 0.15 g, p-methoxyphenol: 0.
15 g and 50 g of dioxane were added, and under nitrogen atmosphere, 50-
The reaction was performed at 60 ° C. for 2 hours.

Next, the liquid isoprene "TL-20" (
197 g of Kuraray Co., Ltd. was dissolved in 300 g of dioxane, and this solution was further added to the above reaction solution, and reacted at 50 to 60 ° C. for 5 hours under a nitrogen atmosphere. From the infrared absorption spectrum, it was confirmed that the absorption of the isocyanate group (2250 cm ^-1 ) had disappeared, and the reaction was terminated. Next, dioxane was removed with a vacuum dryer to obtain a solid polymer. 3300, 2920, 1710, 1640
Characteristic absorption was observed at cm ⁻¹ . The structural formula of this polymerizable rubber is shown.

[0042]

Embedded image

Example 6 In a 1 liter reactor described in Example 1, 2,4-tolylene diisocyanate R
² (NCO) ₂ : 69.6 g and neopentyl glycol R ³
(OH) ₂ : 20.8 g was dissolved in 150 g of dioxane. The temperature of this solution was maintained at 50 to 60 ° C., and the reaction was performed under a nitrogen atmosphere for 3 hours. Then, 59.6 g of pentaeristol triacrylate, 0.16 g of triethylenediamine, 0.15 g of p-methoxyphenol and 50 g of dioxane were added,
The reaction was carried out at 50-60 ° C. for 2 hours under a nitrogen atmosphere.

Next, the liquid isoprene "TL-20" (
260 g (manufactured by Kuraray Co., Ltd.) was dissolved in 300 g of dioxane, and this solution was further added to the above reaction solution, and reacted at 50 to 60 ° C. for 5 hours under a nitrogen atmosphere. From the infrared absorption spectrum, it was confirmed that the absorption of the isocyanate group (2250 cm ^-1 ) had disappeared, and the reaction was terminated. Next, dioxane was removed with a vacuum dryer to obtain a solid polymer. 3300, 2920, 1710, 1640
Characteristic absorption was observed at cm ⁻¹ . The structural formula of this polymerizable rubber is shown.

[0045]

Embedded image

Example 7 In a 1 liter reaction vessel described in Example 1, hexamethylene diisocyanate R ² N
CO ₂ : 33.6 g and 1,4-butanediol R ³ (OH)
₂ : 9 g was dissolved in 100 g of dioxane. The temperature of this solution was maintained at 50 to 60 ° C., and the reaction was performed under a nitrogen atmosphere for 3 hours. Then, dipentaeristol monohydroxypentaacrylate: 52.4 g, triethylenediamine: 0.18
g, hydroquinone: 0.18 g and dioxane 100 g were added and reacted at 50-60 ° C. for 2 hours under a nitrogen atmosphere.

Next, the liquid isoprene “TL-20” (
260 g (manufactured by Kuraray Co., Ltd.) was dissolved in 300 g of dioxane, and this solution was further added to the above reaction solution, and reacted at 50 to 60 ° C. for 5 hours under a nitrogen atmosphere. From the infrared absorption spectrum, it was confirmed that the absorption of the isocyanate group (2250 cm ^-1 ) had disappeared, and the reaction was terminated. Next, dioxane was removed with a vacuum dryer to obtain a solid polymer. 3300, 2920, 1710, 1640
Characteristic absorption was observed at cm ⁻¹ . The structural formula of this polymerizable rubber is shown.

[0048]

Embedded image

(Comparative Example 1) In the 1 liter reaction vessel shown in Example 1, 34.8 g of 2.4-tolylene diisocyanate R ² (OH) ₂ , 11.6 g of 2-hydroxyethyl acrylate and 0.15 g of g of triethylenediamine (urethanization catalyst) and 0.15 g of p-methoxyphenol (polymerization inhibitor) were dissolved in 250 g of dioxane. The temperature of this solution was maintained at 50 to 60 ° C., and the reaction was performed for 3 hours in a nitrogen atmosphere. Thus, the following monoisocyanate compound was obtained.

[0050]

Embedded image

Next, the liquid butadiene rubber "R-45H"
T ”(made by Idemitsu Petrochemical Co., Ltd.)
0 g, this solution was further added to the above reaction solution,
The reaction was carried out at 50-60 ° C for 5 hours under a nitrogen atmosphere. From the infrared absorption spectrum, the absorption of isocyanate group (2250c
After confirming that m ^-1 ) had disappeared, the reaction was terminated. Next, dioxane was removed with a vacuum dryer to obtain a viscous polymer. When measured by infrared absorption spectrum, 3300, 292
Characteristic absorption was observed at 0, 1710, and 1640 cm ^-1 . The structural formula of this polymerizable rubber is shown.

[0052]

Embedded image

Comparative Example 2 58.0 g of isophorone diisocyanate R was placed in the 1 liter reaction vessel shown in Example 1.
² (OH) ₂ , 15.1 g of 2-hydroxyethyl acrylate, 0.15 g of dibutyltin dilaurate and 0.15 g of p
-Methoxyphenol was dissolved in 250 g of dioxane. The temperature of this solution was maintained at 50 to 60 ° C., and the reaction was performed for 3 hours in a nitrogen atmosphere. Next, a solution prepared by dissolving 260 g of polytetramethylene ether glycol (PTMEG) in 350 g of dioxane was further added to the above reaction solution, and reacted at 50 to 60 ° C. for 5 hours under a nitrogen atmosphere. From the infrared absorption spectrum, it was confirmed that the absorption of the isocyanate group (2250 cm ^-1 ) had disappeared, and the reaction was terminated. Next, dioxane was removed with a vacuum dryer to obtain a solid polymer. 3300, 2920, 1710, 1640
Characteristic absorption was observed at cm ⁻¹ .

(Formation of Cured Film) The polymer 100 of each of the above examples was used.
Parts by weight were dissolved in 2 parts by weight of benzyl dimethyl ketal (photopolymerization initiator) and 500 parts by weight of tetrahydrofuran to prepare a solution of 602 parts by weight. The solutions of each of these examples were applied to a glass plate, and tetrahydrofuran was evaporated to form a film having a thickness of about 500 μm. The glass plate was placed on a belt conveyor and irradiated with a high-pressure mercury lamp to cure the coating. As a high-pressure mercury lamp, “QRM. 2077 A
(Manufactured by Oak Manufacturing Co., Ltd.) 80 W / cm: a three-light type was used. The height of the ramp was 150 mm, and the conveying speed of the belt conveyor was 6 m / min.

The number average molecular weight, photosensitivity, and adhesion to each substrate of each polymer were measured. In addition, a physical property test of hardness and a tensile test were performed on the cured film of each example.
Table 2 shows the test results. The test method is as follows.

(Number average molecular weight M _n ) Measured by high performance liquid chromatography “GPC” (manufactured by Waters). (Sensitivity) It was measured by the gray scale method. Specifically, a solution composed of 100 parts by weight of each polymer, 2 parts by weight of benzyldimethyl ketal, and 900 parts by weight of tetrahydrofuran was prepared, and this solution was applied on a copper plate and dried at room temperature for 2 hours. A film having a thickness of about 50 μm was obtained. Kodak Step Tablet No. 2 was overlaid, irradiated with a high-pressure mercury lamp (80 W / cm), developed with isophorone for 2 minutes, and the number of insolubilizing stages was determined.

(Adhesion) 100 parts by weight of the polymer of each example, N
-Vinyl-2-pyrrolidone (GAF, photopolymerizable monomer) (50 parts by weight) and benzyldimethyl ketal (4 parts by weight) were mixed, mixed and stirred to obtain a solution. Screen plate (250 mesh, Tetron screen, emulsion thickness 10μ)
m)), each solution was printed on the surface of the substrate. As a material of the base material, a polycarbonate resin, a polyvinyl chloride resin, an ABS resin (acrylonitrile-butadiene-styrene copolymer resin), aluminum, iron, and stainless steel were selected. The surface of the substrate was irradiated with a high-pressure mercury lamp (80 W / cm) to cure the printed film. Next, 100 base lines were formed on the printed film at intervals of 1 mm in length and 1 mm in width, and a cellophane adhesive tape (trade name Nichiban Co., Ltd.
o.405) was pressed, and then the tape was peeled off. After that, the remaining number of the 100 base lines was examined.

(Tensile test) By performing a tensile test in accordance with JIS K 7113, the tensile strength, elongation,
The tear strength was measured. The tensile speed was 100 mm / min.

(Developability) 100 parts by weight of the polymer of each example, 2 parts by weight of benzyldimethyl ketal, and 9 parts of tetrahydrofuran
00 parts by weight, and apply this solution to the surface of a copper plate,
After drying at room temperature for 2 hours, a coating having a thickness of 50 μm was obtained. The negative film loaded with the image was brought into close contact with the dried film, and then irradiated with a high-pressure mercury lamp (80 W / cm) to perform exposure. After removing the negative film, the resin layer was developed in water using a nylon brush for 1 minute. As a result, when the unexposed portion was completely dissolved and removed, and a cured film pattern faithful to the original image could be formed, the evaluation was "〇".
When a clear image was not obtained because the unexposed portion remained considerably adhered, it was evaluated as “x”.

(Water-soluble) 1 g of each polymer was precisely weighed, and 100 ml of water was added thereto, followed by stirring at room temperature for 24 hours. Next, the whole was filtered through a 200-mesh wire mesh, and the residue remaining on the wire mesh was
Vacuum dried at 24 ° C. for 24 hours. The ratio of insoluble content was calculated according to the following equation.

## EQU1 ## Insoluble content ratio (%) = weight of residue after vacuum drying
(g) × 100/1 (g)

[0061]

[Table 2]

As can be seen from Table 2, in Examples 1 to 7, the sensitivity of the polymerizable rubber, the adhesive strength to the substrate, the tensile strength, the elongation, and the tear strength of the cured film are high. Further, it has good developability and high water solubility.

Next, 10 g of the polymerizable rubber obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were weighed. 50 g of the polymerizable monomer shown in Table 3 was added thereto, stirred at room temperature for 30 hours, and the state after mixing was observed. When no precipitate or insoluble matter was observed and a clear solution was obtained, the evaluation was "〇". When no precipitate or insoluble matter was observed and a cloudy solution was obtained, the evaluation was “Δ”. When a precipitate and an insoluble matter were observed, it was evaluated as “x”. Table 3 shows the results of these evaluations.
Shown in

[0064]

[Table 3]

As can be seen from Table 3, the polymerizable rubbers of Examples 1 to 7 have high compatibility with various polymerizable monomers. In particular, Examples 4 and 7 are the best, and Examples 2, 5, and 6 are second to this.

[0066]

As described above, the polymerizable rubber of the present invention cures well alone or in combination with other polymerizable monomers. The cured film was tough and flexible, and had a high adhesive strength to substrates such as metals and plastics. Moreover, the polymerizable rubber of the present invention has high compatibility with various polymerizable monomers, so it is extremely easy to handle and practical, and dissolves well in solvents other than chlorine-based. It can be used as a mold flexographic plate material and as a raw material for photoresist. Moreover, because of its high hydrophilicity, it can be used for water development of flexographic plate materials, photoresists and the like.

Continuation of the front page (56) References JP-A-62-7714 (JP, A) JP-A-58-76414 (JP, A) JP-A-4-77515 (JP, A) JP-A-60-123525 (JP) , A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 18/67, 18/69

Claims (1)

(57) [Claims] 1. A polymerizable rubber having a structural formula represented by the following formula (I). Embedded image [R ¹ represents a hydrogen atom or a methyl group. R ² represents a residue obtained by removing two isocyanate groups from a diisocyanate compound. R ³ represents a residue obtained by removing two hydroxyl groups from a dihydric alcohol having a molecular weight of 500 or less. R ⁴ represents a hydrocarbon group having 2 to 12 carbon atoms or a polyoxyalkylene group having 2 to 12 carbon atoms. l shows the integer of 1-5. m
Represents an integer of 1 or more. n shows the integer of 1-16.
x represents an integer of 1 or more. A represents 10 repeating units
As described above, a diene-based liquid rubber of 1000 or less, wherein (m +
and x) a residue obtained by removing m hydroxyl groups from a diene-based liquid rubber having hydroxyl groups. ]