JPH10279633A - Reactive polymer and composite polymer and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reactive polymer by copolymerizing a (meth)acrylic ester monomer having a photopolymn. initiator group, a monofunctional vinylarom. monomer, a polyfunctional vinylarom. monomer in emulsion while fully utilizing the function of a photopolymn. initiator group and while efficiently polymerizing the monofunctional monomer and the polyfunctional monomer. SOLUTION: This reactive polymer is obtd. by copolymerizing a (meth)acrylic ester monomer represented by formula I (wherein R<1> is H or methyl) having a photopolymn. initiator group, a monofunctional vinylarom. monomer and a polyfunctional vinylarom. monomer in emulsion. A composite polymer is obtd. by subjecting the reactive polymer, a monofunctional acrylic ester monomer represented by formula II (wherein R<2> is 1-20C alkyl), and a polyfunctional (meth)acrylic ester monomer to free-radical polymn. under the exposure to an active energy ray. The wavelength of the active energy ray is pref. 200-800 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel reactive polymer containing a photopolymerization initiating group in a polymer molecule, a method for producing the same, a novel composite polymer derived from the reactive polymer, The present invention relates to the manufacturing method. More specifically, polymer modifiers, polymer alloying agents, polymer compatibilizers, functional molding materials, paints, adhesives, inks, medical materials, cosmetics, fragrances, polymer flocculants, microdispersion aids The present invention relates to a reactive polymer, a composite polymer, and a method for producing the same, which are useful in such fields.

[0002]

2. Description of the Related Art Hitherto, a method for producing a composite polymer having an interpenetrating polymer network structure has been known. For example,
"Journal of Applied Polymer Science", Vol. 29, pp. 2969-2980 (1984), Vol. 31, pp. 1955-1962 (1986), Vol.
3, pp. 215-225 (1987), discloses a formulation of a latex-based interpenetrating polymer network.

Specifically, a cross-linked polymer particle obtained by an emulsion polymerization method is impregnated with a monofunctional monomer and a polyfunctional monomer in a latex, and then emulsion-polymerized again. It is described that an interpenetrating polymer network is formed inside the latex particles.

In Japanese Patent Publication No. 6-99666,
The following composite polymers are disclosed. That is, a polyfunctional monomer containing two or more unsaturated groups having different copolymerizabilities such as allyl acrylate, and a polymerizable monomer such as an alkyl acrylate that undergoes a polymerization reaction with one unsaturated group of the polyfunctional monomer. Emulsion polymerization of the monomer and the crosslinkable monomer.
Next, a vinyl-type monomer that undergoes a polymerization reaction with the other unsaturated group is added to polymer particles having a three-dimensional reactive group in which the other unsaturated group of the polyfunctional monomer remains. And graft polymerization to produce a composite polymer having a linear polymer chain.

[0005]

However, in the former case of the prior art, during the second stage polymerization, polymerization is not necessarily performed only inside the particles, but also outside the particles. It cannot be a polymer with an intrusive network structure,
Some polymers that do not contribute to the mutual network are also formed, which adversely affects the performance of the obtained polymers. That is, the polymer is polymerized outside the polymer to be a very heterogeneous polymer, and thus there is a problem that the mechanical properties are reduced.

In the latter case, the remaining allyl group does not always have good reactivity with the vinyl monomer, and a polymer which does not participate in the formation of a composite polymer is formed, and it is difficult to reliably form an interpenetrating network structure. However, it is difficult to form a polymer having the desired performance.

Further, in any of the above-mentioned techniques, basically, the second stage polymerization is a reaction under heating, and the crosslinked polymer particles polymerized in the first stage are subjected to the polymerization in the second stage. Swells easily due to the heat of the resin, and it is difficult to form a dense and uniform composition interpenetrating network structure. Therefore, there are problems such as a decrease in mechanical properties, and it is a reality that a satisfactory composite polymer cannot be produced yet.

[0008] The present invention has been made in view of the problems existing in the prior art as described above. An object of the present invention is to provide a reactive polymer which can sufficiently exhibit the function of a photopolymerization initiation group and can efficiently polymerize a predetermined monofunctional monomer and polyfunctional monomer. It is in.

Another object is to make it possible to produce a reactive polymer efficiently and to adjust the amount of a predetermined photopolymerization-initiating group-containing monomer so that the amount of the photopolymerization-initiating group can be easily controlled within a desired range. An object of the present invention is to provide a method for producing a reactive polymer that can be set.

Another object of the present invention is to provide a composite polymer which can surely form a dense and uniform composition interpenetrating network structure and sufficiently exhibit properties such as mechanical properties based on the network structure.

Another object of the present invention is to make it possible to produce a composite polymer efficiently and to adjust the charged amounts of a predetermined monofunctional monomer and polyfunctional monomer so that a reactive polymer can be surely produced. An object of the present invention is to provide a method for producing a composite polymer in which the interpenetrating network chain of the composite polymer obtained by polymerizing the molecular chain according to the charged composition can be freely designed.

[0012]

In order to achieve the above-mentioned object, the reactive polymer of the first invention has the following general formula (I)
Is obtained by emulsion polymerization of a (meth) acrylate monomer containing a photopolymerization initiation group, a monofunctional vinyl aromatic monomer and a polyfunctional vinyl aromatic monomer. In this specification, acrylic and methacryl are collectively referred to as (meth) acryl.

[0013]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) A method for producing a reactive polymer according to the second invention is a (meth) acrylic acid containing a photopolymerization initiation group represented by the following general formula (I). Ester monomer, monofunctional vinyl aromatic monomer and polyfunctional vinyl aromatic monomer, heated in the presence of a polymerization initiator,
The emulsion polymerization is performed.

[0014]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) The composite polymer of the third invention is a monofunctional compound represented by the following general formula (II) with respect to the reactive polymer of the first invention. An acrylic acid ester monomer and a polyfunctional (meth) acrylic acid ester monomer are added, and radical polymerization is performed under irradiation with active energy rays.

[0015]

Embedded image (In the formula, R ² represents an alkyl group having 1 to 20 carbon atoms.) A method for producing a composite polymer according to a fourth aspect of the invention includes a photopolymerization initiation group-containing (meth) represented by the following general formula (I). An acrylic acid ester monomer, a monofunctional vinyl aromatic monomer and a polyfunctional vinyl aromatic monomer are heated and emulsion polymerized in the presence of a polymerization initiator, and the obtained reactive polymer is The acrylate monomer represented by the general formula (II) and the polyfunctional (meth) acrylate monomer are added, and radical polymerization is performed under irradiation with active energy rays.

[0016]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.)

[0017]

Embedded image (Wherein, R ² represents an alkyl group having 1 to 20 carbon atoms.) The composite polymer according to the fifth aspect of the present invention is the composite polymer according to the third aspect, in which a polymer network formed by the reactive polymer is irradiated with active energy rays. Has an interpenetrating polymer network structure in which the polymer networks formed by each other are intertwined with each other.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. First, the reactive polymer is a (meth) acrylate monomer containing a photopolymerization initiation group, a monofunctional vinyl aromatic monomer and a polyfunctional vinyl aromatic monomer represented by the following general formula (I). Is obtained by emulsion polymerization.

[0019]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) The reactive polymer is a (meth) acrylic acid ester monomer containing a photopolymerization initiation group represented by the general formula (I), It is produced by heating and emulsion-polymerizing a vinyl aromatic monomer and a polyfunctional vinyl aromatic monomer in the presence of a polymerization initiator.

As the (meth) acrylic acid ester monomer containing a photopolymerization initiation group represented by the general formula (I), which forms a reactive polymer,

[0021]

Embedded image

[0022]

Embedded image And the like. In addition, examples of the monofunctional vinyl aromatic monomer include styrene, α-methylstyrene, p-vinyltoluene, and the like.

Further, examples of the polyfunctional vinyl aromatic monomer include divinylbenzene. General formula (I)
The content of the (meth) acrylate monomer containing a photopolymerization initiating group is 0.05 to 2 parts by weight in 100 parts by weight of the monomer mixture.
It is desirably in the range of 0 parts by weight. The content of this monomer is calculated based on the content of the desired photopolymerization initiating group in the monomer. When the content of this monomer is 0.0
If the amount is less than 5 parts by weight, the photopolymerization initiating group contained in the obtained reactive polymer is too small, and it is difficult to sufficiently exert the function as the reactive polymer. Meanwhile, 2
If the amount exceeds 0 parts by weight, the photopolymerization initiating group introduced into the obtained reactive polymer may cause radical collapse or extreme gelation during the reaction.

The content of the monofunctional vinyl aromatic monomer and the polyfunctional vinyl aromatic monomer forming the reactive polymer is 60 to 99.99 parts per 100 parts by weight of the monomer mixture.
It is preferably 9 parts by weight and 0.05 to 20 parts by weight. Outside of these ranges, it becomes difficult for the composite polymer derived from the reactive polymer to have a uniform and dense interpenetrating network structure, which is not preferable.

The resulting reactive polymer is added with a new acrylate ester when forming a composite polymer, and contained so that it can be polymerized by radical polymerization initiation ability using active energy ray irradiation. The photopolymerization initiation group has a structure in which the photopolymerization initiation group is chemically bonded to the reactive polymer chain itself.

In the method for producing the reactive polymer,
As described above, a specific photopolymerization initiation group-containing (meth) acrylate monomer, a monofunctional vinyl aromatic monomer and a polyfunctional vinyl aromatic monomer are emulsified in the presence of a polymerization initiator. The polymerization is carried out by a conventional method according to a legal method. In this case, the heating temperature is preferably in the range of 35 to 95 ° C. in order to efficiently carry out the emulsion polymerization.

The polymerization initiator used in this case includes, for example, inorganic polymerization initiators such as ammonium persulfate, potassium persulfate, sodium persulfate, peracid, and hydrogen persulfide; A system of a polymerization initiator obtained by combining a ferrous salt such as ferrous iron, ferrous chloride, and ferrous acetate, or a reducing agent such as sodium acid sulfite, sodium thiosulfate, and Rongalite; Isobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid, 1-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'- Azo compounds such as azobisisobutyrate; t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, acetyl peroxide Oxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, dicumyl peroxide, di-t-
Butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis (t
-Butyltyloxy) cyclohexane, 1,1-bis (t-butylperoxin) -3,3,5-trimethylcyclohexane, isobutyryl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di- organic peroxides such as n-propylperoxydicarbonate, t-butylperoxyneodecanate and cumylperoxyneodecanate; dimethylaniline, ferrous sulfide, ferrous chloride, acetic acid Examples thereof include ferrous salts such as ferrous iron, or a polymerization initiator system in which a reducing agent such as sodium acid sulfite, sodium thiosulfate, or Rongalite is combined.

In particular, in the case of the emulsion polymerization method, an inorganic polymerization initiator such as ammonium persulfate, potassium persulfate, sodium persulfate, persulfuric acid, hydrogen peroxide, etc .;
A polymerization initiator system combining a ferrous salt such as ferrous chloride and ferrous acetate, a reducing agent such as sodium acid sulfite, sodium thiosulfate, and Rongalite; t-butyl vidropperoxide, cumene hydroperoxide; Combination of hydroperoxides such as diisopropylbenzene vidroperoxide, and ferrous salts such as ferrous sulfate, ferrous chloride, and ferrous acetate, and reducing agents such as dimethylaniline, sodium acid sulfite, sodium thiosulfate, and Rongalite. Polymerization initiators such as those of the above polymerization initiators are preferred.

The amount of the polymerization initiator used is preferably in the range of 0.001 to 20 parts by weight based on 100 parts by weight of the total monomers used as raw materials. Since this reactive polymer is obtained by an emulsion polymerization method, it is in the form of particles, and the average particle diameter is preferably in the range of 0.01 to 1000 μm. If the average particle size is less than 0.01 μm, the viscosity of the emulsion at the time of production increases, and the workability decreases. On the other hand, if it exceeds 1000 μm, good smoothness cannot be obtained when used for paints or inks, and the sedimentation stability tends to be further reduced.

In order to adjust the particle size of the reactive polymer particles within the above-mentioned average particle size range of 0.01 to 1000 μm, for example, a surfactant, a dispersion stabilizer, a polymer surfactant, Can be carried out by appropriately selecting the synthesis conditions such as the type and amount of the compound, the type of the dispersion medium and the monomer, the type of the polymerization initiator, the dropping rate, and the polymerization temperature.

Next, the composite polymer is composed of a monofunctional acrylate monomer represented by the following general formula (II) and a polyfunctional (meth) acrylate monomer with respect to the reactive polymer. And radical polymerization under irradiation with active energy rays.

[0032]

Embedded image (In the formula, R ² represents an alkyl group having 1 to 20 carbon atoms.) Examples of the monofunctional acrylate monomer used when producing the composite polymer using the reactive polymer include:
Methyl acrylate, ethyl acrylate, acrylic acid n-
Propyl, iso-propyl acrylate, n-acrylate
-Butyl, iso-butyl acrylate, acrylic acid se
Examples include c-butyl, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, and the like.

Of these, methyl acrylate, ethyl acrylate, n-propyl acrylate, isyl acrylate
1 to 1 carbon atoms such as o-propyl and n-butyl acrylate
Acrylic esters comprising 4 lower alkyl groups are preferred. The reason is that the glass transition point of the obtained composite polymer is in an appropriate range, and the function based on the interpenetrating polymer network structure can be sufficiently exhibited.

The polyfunctional (meth) acrylic acid ester monomer includes ethylene glycol di (meth)
Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diacrylphthalate, allyl (meth) acrylate, 2-hydroxy-
1,3-di (meth) acryloxypropane, 2,2-bis (4-((meth) acryloxyethoxy) phenyl)
Propane, trimethylolpropane tri (meth) acrylate, tetramethylol methane (meth) acrylate, pentaerythritol tri (meth) acrylate,
Examples thereof include dipentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tetramethylolmethanetetra (meth) acrylate.

Of these, neopentyl glycol di (meth) acrylate is most preferable because a composite polymer having an interpenetrating polymer network structure can be efficiently produced.

Monofunctional acrylate monomer and polyfunctional (meth) used in forming the above-mentioned composite polymer
The acrylate monomer is preferably in the range of 5 to 400 parts by weight and 0.1 to 100 parts by weight, respectively, based on 100 parts by weight of the reactive polymer. Outside of this range, it becomes difficult for the composite polymer to form a uniform and dense interpenetrating network structure, which is not preferable.

In the production of a composite polymer using a reactive polymer, specifically, the above monofunctional acrylate monomer and polyfunctional (meth) acrylate monomer are dispersed in an emulsion as it is. The reaction is carried out by impregnating the reactive polymer and subjecting it to radical polymerization under irradiation with active energy rays. Further, after the emulsion polymerization, the reactive polymer is taken out of the emulsion and dried, and in a bulk state where the monofunctional acrylate monomer and the polyfunctional (meth) acrylate monomer are added, or further there. Radical polymerization can also be performed under irradiation with active energy rays in a state where an organic solvent is added.

The condition for irradiating the active energy ray is not particularly limited as long as it can absorb the photopolymerization initiating group, but the wavelength of the active energy ray is preferably in the range of 200 to 800 nm, more preferably in the range of 300 to 600 nm. . Examples of light sources that can be used include mercury lamps, sunlight, hydrogen discharge tubes, xenon lamps, flash discharge tubes, tungsten lamps, halogen lamps, and various lasers such as dye lasers, excimer lasers, and ion lasers.

The thus obtained composite polymer is obtained by adding a new acrylate to the reactive polymer and irradiating it with an active energy ray to form a photopolymerization initiator group chemically bonded to the reactive polymer chain. It is obtained by radical cleavage and polymerization. That is, this composite polymer has an interpenetrating network structure [IPN] in which a vinyl aromatic polymer network made of a reactive polymer and a (meth) acrylate polymer network formed by irradiation with active energy rays are interlaced. (Interpenetrating polymernetwor
k)]. By having such an interpenetrating network structure, functions such as mechanical properties can be improved.

This composite polymer can be used as a composition diluted or dispersed with water or an organic solvent, and can be used as a polymer modifier, a functional molded material, a paint, an adhesive, an ink, It can be used in a wide range of fields such as medical materials, cosmetics, fragrances, and polymer flocculants.

According to the above embodiment, the following effects are exhibited. According to the reactive polymer of the embodiment, by the function of the photopolymerization initiation group contained in the reactive polymer, that is, by a polymer radical generated at room temperature by irradiation with active energy rays,
The monofunctional acrylate monomer and the polyfunctional (meth) acrylate monomer can be efficiently polymerized.

For this reason, the monomer is surely polymerized and bonded to the polymer molecular chain of the reactive polymer without swelling of the polymer chain unlike the conventional polymerization under heating. In addition, since a polymer that does not contribute to the formation of the composite polymer is not formed as a heterogeneous composition by-produced, a composite polymer having a dense and uniform composition and having an interpenetrating network structure can be obtained. According to the method for producing a reactive polymer, a specific photopolymerization initiation group-containing (meth) acrylate monomer represented by the general formula (I) is used. This makes it possible to easily set the amount of photopolymerization initiating group to be contained in the obtained reactive polymer in a desired range, as compared with a conventional reactive polymer in which an allyl group or the like is left. -Further, according to the composite polymer, it is possible to have a dense and uniform interpenetrating network structure, so that a polymer which does not contribute to the formation of the composite polymer unlike the conventional one, and which lowers the mechanical properties. Can be avoided as a byproduct.

For this reason, the composite polymer can be used for a wide range of applications such as polymer improvers, functional molding materials, paints, adhesives, inks, medical materials, cosmetics, fragrances, and polymer flocculants. Become. According to the method for producing a composite polymer, a monofunctional acrylate monomer and a polyfunctional (meth) acrylate monomer are added to the reactive polymer to which the photopolymerization initiating group is bonded. Polymerization is performed under irradiation of active energy rays by adjusting the charged amount.

Therefore, the polymer chains are surely polymerized and bonded to the polymer molecular chains of the reactive polymer in accordance with the charged composition without swelling unlike the conventional polymerization under heating. The interpenetrating network chains of the resulting composite polymer can be freely designed. The composite polymer has high mechanical properties because it has an interpenetrating network (IPN) in which the polymer network of the reactive polymer and the polymer network formed by the irradiation of active energy rays are interlaced with each other. Performance can be reliably demonstrated. Therefore, it can be applied to a wide range of applications such as polymer improvers, functional molded material materials, paints, adhesives, inks, medical materials, cosmetics, fragrances, and polymer flocculants.

[0045]

EXAMPLES Hereinafter, the above embodiments will be described more specifically with reference to Examples, but the present invention is not limited thereto. The abbreviations in the text and tables are as follows. PI: 1- [4- {2- (2- (methacryloyloxy) ethoxycarbonyloxy) ethoxy} phenyl]
-2-Hydroxy-2-methylpropan-1-one S
T: Styrene BA: Butyl acrylate DVB: Divinylbenzene NPGDA: Neopentyl glycol diacrylate SLS: Sodium lauryl sulfonate ACVA: 4,4'-azobis (4-cyanovaleric acid) (Example 1, Production of reactive polymer) In a 2 liter reaction vessel equipped with a stirrer, a thermometer, a purge gas inlet, and a water-cooled condenser, 474 g of deionized water and 6 g of SLS were charged, heated to 75 ° C. under nitrogen gas aeration, and then stirred.
ST109g, DVB5.8g, PI6g, and ACV
A4.1 g of the mixture was added dropwise over 3 hours. After dripping,
Stirring was continued for 4 hours to complete the polymerization.

When the obtained polymer was measured by an ultraviolet (UV) absorption spectrum, it was found that the photopolymerization initiating group had a wavelength of 340 nm.
It was confirmed from the absorption of that that the same amount of the photopolymerization initiating group as the charged amount had been introduced into the polymer. The particle size of the thus obtained reactive polymer particles was measured according to photon correlation spectroscopy. Further, the glass transition point (° C.) of the obtained reactive polymer was measured by a modulation type differential scanning calorimeter (DSC). The results are shown in Table 1. (Examples 2 to 5, Comparative Examples 1 and 2) A reactive polymer was synthesized by the method described in Example 1 except that the charged composition described in Table 1 was used. Was evaluated. The results are shown in Table 1. In Tables 1 to 3, Darocure 1173 is a photopolymerization initiator manufactured by Ciba-Geigy.

[0047]

[Table 1] As shown in Table 1, in Examples 1 to 5, the polymerization of the monomer used as the raw material was almost completed, and the polymerization of the (meth) acrylic acid ester monomer containing the photopolymerization initiating group used was further completed. It can be seen that 95% or more of the polymerization initiating group remains.

On the other hand, in Comparative Example 1, the photopolymerization initiating group was not present in the obtained polymer because the photopolymerization initiating group-containing (meth) acrylate monomer was not used. In Comparative Example 2, since the polyfunctional vinyl aromatic monomer was not included at the time of polymerization, the glass transition point of the obtained reactive polymer was low, and it was found that the polymer molecular chain was hard to be dense. Example 6 Production of Composite Polymer 1 g of reactive polymer powder isolated from the emulsion of a reactive polymer containing a photopolymerization initiation group obtained by the emulsion polymerization method of Example 1
Was impregnated with a mixed solution of 0.9 g of BA and 0.1 g of NPGDA. Thereafter, this was sandwiched between glass plates, and the glass plate was irradiated with a high-pressure mercury lamp “HPW125W” manufactured by Philips for 15 minutes, and photo-bulk polymerization was performed as shown in FIG.

That is, as shown in FIG. 1, a transparent film 2 made of polyethylene terephthalate is interposed between a pair of glass plates 1a and 1b. On both sides between the transparent film 2 and one of the glass plates 1a, a pair of spacers 3 for maintaining a constant interval is disposed, and a sample 4 made of a reactive polymer powder is disposed between the spacers 3. Is arranged. One glass plate 1a
A high-pressure mercury lamp 5 is disposed above the
V) is irradiated through the glass plate 1a.

Then, the transparent film 2 and a pair of spacers 3 are arranged between the two glass plates 1a and 1b, and the sample 4 is arranged between the spacers 3 and overlapped. Is irradiated.

At this time, the distance from the tip of the lamp 5 to the sample 4 was 20 cm. The obtained composite polymer had no monomer odor and the polymerization was completed. When the glass transition point of the obtained composite polymer was measured by a modulating DSC, the peak of the glass transition point on the high temperature side due to the reactive polymer in the first stage and the polymer composed of BA and NPGDA in the second stage were obtained. , Two of the peaks of the glass transition point on the low temperature side are shown, which were 100 ° C. and 2 ° C., respectively.

[0052]

[Table 2] As shown in Tables 1 and 2, the glass transition point of the reactive polymer of Example 1 was 122 ° C., and the glass transition temperature of the polymer obtained by photopolymerization only from BA and NPGDA of Comparative Example 3 in Table 3. It is clear that the peaks of the composite polymer of Example 6 are closer to each other as compared to the point -8 ° C. Accordingly, the polymer networks of each other were more closely entangled, and the existence of an interpenetrating network structure having a dense and uniform composition was revealed. (Examples 7 to 11, Comparative Examples 3 and 4) In Examples 7 to 10, a composite polymer was synthesized by the method described in Example 6, except that the charged compositions described in Tables 2 and 3 were used. The physical properties were evaluated in the same manner as in Example 6. In Example 11, 5 g of the emulsion containing particles of the reactive polymer having a photopolymerization initiation group obtained in Example 1 was added to BA 0.9.
g of NPGDA and 4 g of deionized water were added, sandwiched between glass plates having a cavity containing the emulsion, and irradiated with the same high-pressure mercury lamp “HPW125W” as in Example 6 for 20 minutes. Then, photoemulsion polymerization was performed as shown in FIG.

That is, as shown in FIG. 2, the other glass plate 1 of the pair of glass plates 1a and 1b is used.
A cavity 6 having an arc-shaped cross section is formed in b, and a sample 4 made of an emulsion of a reactive polymer is accommodated in the cavity 6. After the sample 4 is accommodated in the cavity 6 of the glass plate 1b, the two glass plates 1a and 1b are overlapped. Subsequently, the sample 4 is irradiated with ultraviolet light (UV) from the high-pressure mercury lamp 5 through the glass plate 1a.

At this time, the distance from the tip of the lamp 5 to the sample 4 was 20 cm. The obtained composite polymer had no monomer odor and the polymerization was completed. The obtained emulsion was vacuum-dried to obtain a composite polymer powder, and the physical properties were evaluated in the same manner as in Example 6. The results are shown in Tables 2 and 3.

[0055]

[Table 3] As shown in Tables 2 and 3, in Examples 7 to 11, the peaks of the high-temperature side glass transition point and the low-temperature side glass transition point of the obtained composite polymers were very close to each other, and the phase separation It was found that an interpenetrating network structure with a small, dense and uniform composition was formed.

The technical ideas grasped from the above embodiment will be described below. The content of the photopolymerization-initiating group-containing (meth) acrylate monomer represented by the general formula (I) is 0.05 to 20 parts by weight based on 100 parts by weight of the monomer mixture. A method for producing the reactive polymer according to the above.

In the case of such a constitution, the amount of the photopolymerization initiating group in the reactive polymer is maintained in an appropriate range, and the function as the reactive polymer is surely exhibited without causing gelation or the like. Can be. The content of the monofunctional vinyl aromatic monomer and the polyfunctional vinyl aromatic monomer is 60 to 99.5 parts by weight and 0.05 to 20 parts by weight, respectively, in 100 parts by weight of the monomer mixture. Item 3. A method for producing a reactive polymer according to item 2.

In this case, the composite polymer derived from the reactive polymer can have a uniform and dense interpenetrating network structure. The monofunctional acrylate monomer has 1 to 4 carbon atoms
The method for producing a composite polymer according to claim 4, which is an acrylate monomer comprising a lower alkyl group.

With such a constitution, the glass transition point of the obtained composite polymer can be set to an appropriate range, and the function based on the interpenetrating network structure can be sufficiently exhibited.

[0060]

As described above in detail, according to the present invention, the following effects can be obtained. According to the reactive polymer of the first invention, the polymer chain does not swell as in the conventional polymerization under heating, and the monomer is reliably contained in the polymer molecular chain of the reactive polymer. Since they are polymerized and bonded, it is possible to form a composite polymer having a dense and uniform composition and having an interpenetrating network structure.

Further, according to the method for producing a reactive polymer of the second invention, a specific photopolymerization initiation group-containing (meth) acrylic acid ester monomer is used. Compared with a conventional reactive polymer in which an allyl group or the like remains, the amount of the photopolymerization initiating group contained in the obtained reactive polymer can be easily set within a desired range.

Further, according to the composite polymer of the third invention, it is possible to have a dense and uniform composition interpenetrating network structure, a polymer improver, a functional molded material, a paint, an adhesive It can be used for a wide range of applications such as agents, inks, medical materials, cosmetics, fragrances, and polymer flocculants, and can exhibit high performance in mechanical properties and the like.

In addition, according to the method for producing a composite polymer of the fourth invention, it is possible to efficiently produce a composite polymer having a desired interpenetrating network structure. Moreover, since the polymer chains do not swell as in the conventional polymerization under heating, they are surely polymerized and bonded to the polymer molecular chains of the reactive polymer according to the charged composition. The interpenetrating network chains of the coalescence can be designed freely.

According to the composite polymer of the fifth invention,
Since the composite polymer has an interpenetrating network structure, high performance such as mechanical properties can be reliably exhibited.
Therefore, this composite polymer can be applied to a wide range of uses such as a polymer modifier, a functional molded material, a paint, an adhesive, an ink, a medical material, a cosmetic, a fragrance, and a polymer flocculant.

[Brief description of the drawings]

FIG. 1 is an exploded perspective view showing an apparatus for performing optical bulk polymerization.

FIG. 2 is an exploded perspective view showing an apparatus for performing photoemulsion polymerization.

[Explanation of symbols]

 4: Sample composed of a reactive polymer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08F 257/00 C08F 257/00 265/06 265/06 // (C08F 257/00 220: 10) (72) Inventor Hiroshi Omura 1-3-3, Rokukanyama, Taketoyo-cho, Chita-gun, Aichi Prefecture 1 (72) Inventor Douglas James Hurston United Kingdom Leicestershire Quorn Wyvernhoe Drive 22 (72) Inventor Simon Richard Uschbrook United Kingdom North Yorkshire Molton West Luton Maine Street 3

Claims (5)

[Claims] 1. An emulsion polymerization of a (meth) acrylate monomer containing a photopolymerization initiation group, a monofunctional vinyl aromatic monomer and a polyfunctional vinyl aromatic monomer represented by the following general formula (I). A reactive polymer comprising: Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) 2. A photopolymerization-initiating group-containing (meth) acrylate monomer, a monofunctional vinyl aromatic monomer and a polyfunctional vinyl aromatic monomer represented by the following general formula (I) are polymerized. A method for producing a reactive polymer in which emulsion polymerization is performed by heating in the presence of an initiator. Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) 3. A monofunctional acrylate monomer represented by the following general formula (II) and a polyfunctional (meth) acrylate monomer with respect to the reactive polymer according to claim 1. Is a composite polymer obtained by radical polymerization under irradiation of active energy rays with the addition of a polymer. Embedded image (In the formula, R ² represents an alkyl group having 1 to 20 carbon atoms.) 4. The polymerization of a (meth) acrylate monomer, a monofunctional vinyl aromatic monomer and a polyfunctional vinyl aromatic monomer containing a photopolymerization initiating group represented by the following general formula (I) is initiated. Emulsion polymerization is carried out by heating in the presence of an agent, and the resulting reactive polymer is reacted with an acrylate monomer represented by the following general formula (II) and a polyfunctional (meth) acrylate monomer And producing a composite polymer which undergoes radical polymerization under irradiation of active energy rays. Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) (In the formula, R ² represents an alkyl group having 1 to 20 carbon atoms.) 5. A polymer network of the reactive polymer,
The composite polymer according to claim 3, which has an interpenetrating polymer network structure in which polymer networks formed by irradiation with active energy rays are intertwined with each other.