WO2015151949A1 - High-strength elastomer - Google Patents

High-strength elastomer Download PDF

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WO2015151949A1
WO2015151949A1 PCT/JP2015/059066 JP2015059066W WO2015151949A1 WO 2015151949 A1 WO2015151949 A1 WO 2015151949A1 JP 2015059066 W JP2015059066 W JP 2015059066W WO 2015151949 A1 WO2015151949 A1 WO 2015151949A1
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meth
monomer
elastomer
monomer component
acrylate
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河合 道弘
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東亞合成株式会社
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06Polymerisation of acrylate or methacrylate esters on to polymers thereof

Abstract

An elastomer having a (semi)interpenetrating network structure, said elastomer being produced by polymerizing and crosslinking a first monomer component to form a first network structure, then introducing a second monomer component into the first network structure, and then polymerizing or polymerizing and crosslinking the second monomer component, wherein the first monomer component is composed of only a nonionic vinyl monomer, a polymer produced from the second monomer component has a glass transition temperature (Tg) of -80 to 20°C, and the ratio of the mass of the first monomer component to that of the second monomer component is 1/0.1 to 1/30.

Description

High strength elastomer

The present invention relates to an elastomeric high strength. More particularly, to an elastomeric high strength with a (semi) interpenetrating network structure.

Elastomeric materials have been used in various fields of a sealant or packing material such as the beginning of giving good moldability and oil resistance and the like. Among them, an acrylic elastomer mainly composed of acrylic acid ester, transparency, heat resistance and automotive parts of the seal since it is excellent in weather resistance, gaskets, is also used in the housing or the like of the adhesive products materials and home appliances . Moreover, automobile tires, when used as various industrial materials such as building materials and medical materials, since the elastomeric material of high strength is required by for improving the reliability and durability, to improving the strength of the elastomer various studies have been made.

Patent Document 1, a mixture containing a specific thermoplastic resin and an acrylic elastomer serving acrylic rubber, thermoplastic elastomer formed by dynamically heat-treated under crosslinking agent there is disclosed. Further, Patent Document 2, block copolymer containing methacrylic ester polymer block and an acrylic ester polymer block as well as compositions containing acrylic elastomer serving acrylic polymer rubbers are disclosed ing. However, it is to become a mixture comprising acrylic elastomer and other components, difficult to secure sufficient transparency from compatibility problems and the like, in some cases there is the bleeding problems. As described above, study on improving the strength of the acrylic elastomer are many due to mixing with other polymers and fillers, etc., necessary to increase the strength by polymer itself constituting the acrylic elastomer is small.
On the other hand, it has an appropriate elongation, and, as a high strength material, (semi) hydrogel or organogel having an interpenetrating network structure (DN structure) has been disclosed (Patent Documents 3-5). Also, after obtaining the first network from the ionic monomer containing a specific quaternary salt structure nonionic monomers, elastomers with DN structure obtained by forming a second network has also been proposed (Non Patent Document 1).

JP 2006-124538 JP International Publication No. WO 2002/081561 International Publication No. WO 2003/093337 JP 2010-111821 JP JP 2012-1596 JP

" Polymer debate Proceedings ", 62, No.2,3157-3158 (2013)

However, hydrogel or organogel described in Patent Documents 3-5, since those containing a medium such as water or an organic solvent, properties such as strength there is a problem that unstable by their content media are different. Further, the volatilization and bleeding like the media, was also intended over time its performance is feared to vary. Further, the elastomer described in Non-Patent Document 1, although showing good strength are those that do not contain medium was achieved, resulting in a large hysteresis loss when added tensile stress and the like. Therefore, if the release and load stress is used in applications such as repeated were those durability as material is a problem.

The present invention has been made in view of such circumstances, an elastomer showing a very high strength without depending on the mixing with other polymers and fillers, etc., when added tensile stress, etc. it is an object of the present invention also provides a free acrylic elastomer be causing hysteresis loss.

The present inventor has conducted extensive studies to solve the above problems, shows the elastomer high strength with a (semi) interpenetrating network structure according to a particular configuration, and also the hysteresis loss when added tensile stress suppression and it is found to be, and have completed the present invention.

That is, the first invention, after forming the first network structure by polymerization and crosslinking a first monomer component, introducing a second monomer component into the network structure of the first , polymerization, or polymerization and an elastomer having obtained (semi) interpenetrating network structure by crosslinking,
The first monomer component consists only nonionic vinyl monomer,
It said second glass transition temperature of the polymer obtained from monomer component (Tg) is the -80 ~ 20 ° C.,
The weight ratio of the first monomer component and the second monomer component, an elastomer is a 1 / 0.1 to 1/30.

The second aspect of the invention, in the first monomer component, the first invention using a crosslinkable monomer 0.01 ~ 2 mol% based on the total amount of the monomers except for the crosslinking monomer an elastomer described.
A third aspect of the invention, in the second monomer component, the first invention or the used 0 ~ 2 mol% of crosslinking monomer based on the total amount of the monomers except for the crosslinking monomer an elastomer according to second invention.
The fourth invention, the second monomer component, an elastomer according to any of the first invention to third invention comprising a compound represented by the following general formula (1) or 80 mol% is there.

Figure JPOXMLDOC01-appb-C000002
Wherein, R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkoxyalkyl group of the alkyl group or a C 2-8 1-8 carbon atoms. ]

Acrylic elastomer of the present invention exhibit a very high strength. Also, without causing hysteresis loss due to stress of the tensile or the like, a material excellent in durability. Furthermore, since there is no need to mix other polymers and fillers, etc., it is possible to avoid the problem derived from the compatibility or bleeding, etc. of these components. In addition, because it is not intended to include media such as water or an organic solvent, it becomes capable of exerting a stable over time performance.

It is a graph showing the repeated tensile test results performed on elastomer obtained in Example 4. Is a graph showing the repeated tensile test results performed on the elastomer obtained in Example 9. Repeated tensile test results performed on elastomer obtained in Comparative Example 5 is a graph showing a.

The present invention will be described in detail. In the present specification, "(meth) acrylic" means acrylic and / or methacrylic, and "(meth) acrylate" means acrylate and / or methacrylate. Further, "(meth) acryloyl group" means acryloyl group and / or a methacryloyl group.

Elastomers of the present invention, the step of forming the first network structure by crosslinking and polymerizing the first polymer (hereinafter, referred to as "first step"), and a second monomer to the first network structure introducing body composition has polymerized, or polymerized, and the step of cross-linking (hereinafter referred to as "second step") by being manufactured through the a (semi) interpenetrating network structure.
The interpenetrating network structure, meaning and network structure in the first polymer obtained by the first step, the second and the network structure in the polymer is intertwined overall structure obtained by the second step to. When polymerized and crosslinked to the second monomer component in the second step, it is possible to obtain a polymer having an interpenetrating network structure.
The semi-interpenetrating network structure, which means a network structure in the first polymer obtained by the first step, the mutually entangled structure as a whole and the resulting linear polymer by the second step . When polymerizing the second monomer component so as not to cause crosslinking in the second step, it is possible to obtain a polymer having a semi-interpenetrating network structure.
In the present invention referred to as "interpenetrating network structure" and / or "semi-interpenetrating network structure" "(semi) interpenetrating network structure". Further, "interpenetrating network structure" and "semi-interpenetrating network structure" includes not only the first step and the second step, is a concept that is applied to the resulting polymer via a third step of the subsequent step .
Hereinafter, the present invention will be described in detail along each step.

<First Step>
In the first step, first, by polymerizing and crosslinking a first monomer component comprising only nonionic vinyl monomer, a polymer is prepared having the first network structure. Here, the first monomer component is not particularly limited as long as it uses only substantially non-ionic vinyl monomer as a constituent monomer, include ionic compounds as impurities in the raw material it may be.

The nonionic vinyl monomer, a nonionic (meth) acrylic monomer can be suitably used, (meth) acrylic acid alkyl ester compound, (meth) acrylic acid alkoxyalkyl ester compounds, amide group-containing (meth) acrylic monomer, an amino group-containing (meth) acrylic monomers, hydroxyl group-containing (meth) acrylic monomer and terminal alkoxy polyalkylene glycol mono (meth) acrylate is used . Further, the (meth) Besides acrylic monomers, vinyl acetate, N- vinyl formamide, N- vinyl acetamide, may be used N- vinylpyrrolidone and other vinyl monomers such as styrene.
Ratio of the first monomer in the entire component (meth) acrylic monomer is preferably in the range from the viewpoint of 10 ~ 100 mol%, such as transparency and weathering resistance, the range of 30 ~ 100 mol% is and still more preferably in the range of 50 ~ 100 mol%.

Specific examples of the (meth) acrylic acid alkyl ester compound, (meth) acrylate, (meth) acrylate, (meth) acrylate, isopropyl (meth) acrylate n- propyl, (meth) acrylic acid n - butyl, isobutyl (meth) acrylate, butyl (meth) tert- acrylate, (meth) acrylate, 2-ethylhexyl (meth) acrylate n- octyl, isooctyl (meth) acrylate, (meth) acrylic acid n - nonyl, isononyl (meth) acrylate, (meth) having an alkyl group having 1 to 12 carbon atoms such as acrylic acid decyl, and dodecyl (meth) acrylate (meth) acrylic acid ester compound; (meth) cyclohexyl acrylate and (meth) containing alicyclic alkyl group such as methyl acrylate cyclohexyl (meth) Acrylic acid ester compounds and the like, may be used alone or two or more thereof.
Among these, from the viewpoint of mechanical properties, more (meth) acrylic acid ester compound having an alkyl group having 1 to 12 carbon atoms are preferred, having an alkyl group of 1 to 8 carbon atoms (meth) acrylic acid ester compound preferably, acrylic acid ester compound having an alkyl group having 1 to 8 carbon atoms is more preferred.

Specific examples of the (meth) acrylic acid alkoxyalkyl ester compounds, (meth) acrylic acid methoxymethyl, (meth) acrylic acid ethoxymethyl, include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate , it can be used alone or in combination of two or more thereof.

Specific examples of the amide group-containing (meth) acrylic monomer, (meth) acrylamide, tert- butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- isopropyl (meth) acrylamide, N, N- dimethylaminopropyl (meth) acrylamide and (meth) acryloyl morpholine and the like, may be used alone or two or more thereof.

Specific examples of the amino group-containing (meth) acrylic monomer, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and N, N- dimethylaminopropyl (meth) acrylamide and the like, may be used alone or two or more thereof.

Specific examples of the hydroxyl group-containing (meth) acrylic monomer, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylate, 3-hydroxypropyl, 4-hydroxybutyl (meth) acrylate and polyethylene glycol mono ( meth) acrylate and the like, may be used alone or two or more thereof.

Specific examples of terminal alkoxy polyalkylene glycol mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, methoxy polypropylene glycol mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate and ethoxy polypropylene glycol mono (meth) acrylate and the like, may be used alone or two or more thereof.

Further, in order to crosslink the first monomer consisting of component polymers, crosslinkable monomer radical-polymerizable unsaturated groups having 2 or more non-ionic polyfunctional vinyl-based monomer and / or as It may be used non-ionic vinyl monomer having a crosslinkable functional group.
Specific examples of non-ionic polyfunctional vinyl monomers, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified product tri (meth) acrylate, such as di- or tri (meth) acrylates of polyols; methylenebis (meth) acrylamide, bisamides such as ethylenebis (meth) acrylamide, divinylbenzene, there may be mentioned allyl (meth) acrylate, these one or It can be used or two or more.
Among these, alkylene diol di- such dynamic in terms of the physical properties 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and 1,10-decanediol di (meth) acrylate (meth) acrylate.

Specific examples of the nonionic vinyl monomer having a crosslinking functional group, (meth) acrylic acid trimethoxysilyl propyl (meth) acrylate triethoxysilylpropyl (meth) acrylate methyldimethoxysilylpropyl etc. hydrolyzable silyl group-containing (meth) acrylic acid ester compound; N- methylol (meth) acrylamide; N- methoxymethyl (meth) acrylamide, N- butoxymethyl (meth) acrylamide, N- alkoxymethyl (meth) acrylamide etc., and can be used alone or in combination of two or more thereof.

The amount of the crosslinking monomer, the type of non-ionic vinyl monomer to be used, but may vary depending on the resulting elastomer applications, the first monomer excluding a cross-linking monomer preferably from 0.01 ~ 2 mol% based on the total amount of components, more preferably from 0.02 ~ 1.5 mol%, further preferably 0.05 ~ 1 mol%. The amount of the crosslinkable monomer it is possible to obtain an elastomer having high strength equal to or greater than 0.01 mol%. On the other hand, when the amount of crosslinking monomer is too large, it may be difficult advances the introduction of the second monomer component into the first network structure in a second step described below, resulting in (semi) interpenetrating formation of network structure becomes insufficient, the strength of the elastomer does not reach the level that satisfies. If less 2 mol% is used of the crosslinkable monomer, it is possible to obtain a sufficiently high strength elastomer.

In the present invention, it is formed from a first monomer component comprising a first network structure only nonionic vinyl monomer is very important. Thus, even if the addition of tensile stress and the like can be obtained an elastomer without causing hysteresis loss.
If it contains an ionic monomer in the first monomer component may affect the mechanical properties of the elastomer, which may cause hysteresis loss when given a particular tensile stress, etc. . Among ionic monomers, if it contains a monomer containing a quaternary ammonium salt, particularly undesirable because the hysteresis loss is conspicuous.

The polymerization of the first monomer component, it is possible to carry out by a known radical polymerization method can be used, for example, a solution polymerization method, suspension polymerization method, dispersion polymerization method and bulk polymerization. If a solvent is used during the polymerization, a solvent selected from water and various organic solvents may be used depending on the polymerization method. As the organic solvent, cyclic ethers such as tetrahydrofuran and dioxane, benzene, aromatic hydrocarbon compounds such as toluene and xylene, esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone and ketones such as cyclohexanone, orthoformate methyl, methyl orthoacetate, alcohols such as methanol, ethanol and isopropanol are exemplified, can be used alone or in combination of two or more thereof.

The polymerization may be any of aspects thermal and photopolymerization or combinations of these or the like. Among them, photopolymerization is preferable that the polymerization reaction tends to proceed rapidly.
When including a first monomer component to the non-ionic polyfunctional vinyl monomer, also proceed crosslinking parallel polymer by polymerizing a first monomer component, the first network structure is formed. When using non-ionic vinyl monomer having a crosslinkable functional group as a crosslinkable monomer, first by performing a crosslinking reaction by the crosslinking functional group as necessary during or after polymerization it is possible to form a network structure.

If due to thermal polymerization, azo compounds, organic peroxides, can be used a known polymerization initiator such as an inorganic peroxide, it is not particularly limited. It may be used a redox polymerization initiator comprising a known oxidizing and reducing agents.

Examples of the azo compound, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N- butyl-2-methylpropionamide), 2-(tert-butylazo) -2 - cyanopropane, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane) and the like, used alone or two or more of these be able to.

Examples of the organic peroxide, 2,2-bis (4,4-di -t- butyl peroxy cyclohexyl) propane (manufactured by NOF Corporation, trade name "Patetora A"), 1,1-di (t- hexyl peroxy) cyclohexane (the "Perhexa HC"), 1,1-di (t-butylperoxy) cyclohexane (the "Perhexa C"), n-butyl-4,4-di (t-butylperoxy) valerate (the "Perhexa V"), 2,2-di (t-butylperoxy) butane (the "Perhexa 22"), t-butyl hydroperoxide (the "PERBUTYL H"), 1,1,3, 3-tetramethylbutyl hydroperoxide (the "Perocta H"), t-butyl cumyl peroxide (same "Perbutyl C"), di -t- butyl peroxide (same "Perbutyl D" , Di -t- hexyl peroxide (same "Perhexyl D"), di (3,5,5-trimethyl hexanoyl) peroxide (same "Peroyl 355"), dilauroyl peroxide (the "Peroyl L"), bis (4-t-butylcyclohexyl) peroxydicarbonate (the "Peroyl TCP"), di-2-ethylhexyl peroxydicarbonate (the "Peroyl OPP"), di -sec- butyl peroxydicarbonate (same " PEROYL SBP "), cumyl peroxyneodecanoate (the" Percumyl ND "), 1,1,3,3-tetramethylbutyl peroxyneodecanoate (the" Perocta ND "), t-hexyl peroxy neodecanoate (the "Perhexyl ND"), t- butyl peroxy neodecanoate Noe Doo (same "Perbutyl ND"), t- butyl peroxy neo-heptanoate (the "Perbutyl NHP"), t- hexyl peroxypivalate (the "Perhexyl PV"), t- butyl peroxypivalate (same "Perbutyl PV"), 2,5-dimethyl-2,5-di (2-ethyl hexanoyl) hexane (the "Perhexa 250"), 1,1,3,3-tetramethylbutyl peroxy-2-ethyl hexanoate (the "Perocta O"), t-hexyl peroxy-2-ethylhexanoate (the "Perhexyl O"), t-butyl peroxy-2-ethylhexanoate (the "Perbutyl O") , t- butyl peroxy laurate (same "PERBUTYL L"), t- butyl peroxy-3,5,5-trimethyl hexanoate (same "Perbutyl 355 "), t-hexyl peroxy isopropyl monocarbonate (the" Perhexyl I "), t-butyl peroxy isopropyl monocarbonate (the" Perbutyl I "), t-butyl peroxy-2-ethylhexyl monocarbonate (the" PERBUTYL E "), t-butyl peroxy acetate (up" Perbutyl A "), such as t-hexyl peroxybenzoate (the" Perhexyl Z ") and t-butyl peroxybenzoate (the" Perbutyl Z ") can be mentioned , it can be used alone or in combination of two or more of these.

Examples of the inorganic peroxides, potassium persulfate, sodium persulfate, ammonium persulfate, and the like.
As the redox type polymerization initiator, sodium sulfite, and sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, and a reducing agent ferrous sulfate, potassium peroxodisulfate, hydrogen peroxide, tert- butyl hydroperoxide can be used in which the oxide or the like and an oxidizing agent.

The preferred amount of the polymerization initiator, when the total amount of the first monomer and 100 parts by weight, from 0.001 to 1 part by weight, more preferably 0.01 to 1 part by weight. Further, in the case of thermal polymerization, the kind of the monomers used, depending on conditions of concentration, etc., the polymerization temperature is preferably 20 ~ 0.99 ° C., more preferably 40 ~ 100 ° C.. The polymerization time is preferably 0.5 to 20 hours, more preferably 1 to 10 hours.

It can also be used a general photopolymerization initiator case of photopolymerization. Specific examples of 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl - phenyl - ketone, 2-hydroxy-2-methyl-1-phenyl - propane-1-one, 1- [4- (2-hydroxyethoxy) - phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopronone bread-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butan-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) benzyl] phenyl -2-methyl - acetophenone compounds of propan-1-one and the like; benzophenone, 4-phenyl benzophenone, 2,4,6-trimethyl benzophenone and 4-benzoyl-4'-methyl - benzophenone compounds such as diphenyl sulfide; methylbenzoyl formate, oxy-phenyl acetic acid 2- (2-oxo-2-phenyl-acetoxy) ethyl ester and oxy-phenyl acetic acid 2- (2-hydroxyethoxy) ethyl ester of α- keto ester compound; 2,4 , 6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide and the like Phosphine oxide compounds; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin compounds such as benzoin isopropyl ether and benzoin isobutyl ether; titanocene compound; 1- [4- (4-benzoyl) phenyl] -2- acetophenone / benzophenone hybrid-based photoinitiator such as methyl 2- (4-methyl-phenylsulfinyl) propan-1-one; 2-(O-benzoyl oxime) -1- [4- (phenylthio)] - 1,2 oxime ester-based photopolymerization initiators such as octane-dione; and camphor quinone, and the like. Further, preferred amount of the photopolymerization initiator that can be used in combination photosensitizer such as benzophenone, when the total amount of the first monomer and 100 parts by weight, 0.001 to 1 part by weight There, more preferably 0.005 to 0.1 part by weight

Further, in the case of photopolymerization, as the active energy ray irradiation, electron beam, ultraviolet rays, there may be mentioned visible light and X-rays, it is possible to use an inexpensive device, ultraviolet rays are preferred.
UV irradiation device is not particularly limited, for example, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamp, ultra-high pressure mercury lamp, a metal halide lamp, black light lamps, UV electrodeless lamp, LED and the like.
The irradiation intensity is intended to be appropriately adjusted, it is appropriate 0.01 ~ 100mW / cm 2. A more preferred range of irradiation intensity is 0.01 ~ 30mW / cm 2, furthermore preferably 0.01 ~ 5mW / cm 2. The irradiation intensity may be during the polymerization reaction constant may be stepwise or continuously changed. In some situations the polymerization reaction, reaction middle may be stopped temporarily irradiation.

In the present invention, if not using a solvent in the first step, the resulting polymer having a first network structure has is cut or crushed into an appropriate shape if necessary, or a suitable solvent to dissolve or disperse It is in a state subjected to the second step. When using a solvent in the first step, a polymer having a first network structure obtained is subjected to the second step after adding or distilling off the appropriate solvent depending on intact, or require that.

<Second Step>
In the second step, a second monomer component in addition to the polymer obtained in the first step, the polymerization after introducing the second monomer component in the first network structure, or polymerization and crosslinking producing (semi) polymer having an interpenetrating network structure (elastomer) by.
The second monomer component, may be used various vinyl unsaturated compound having a radical polymerizable, follows from the viewpoint of polymer suitable elastomer having elasticity and flexibility can be obtained compound represented by the general formula (1) are preferred.

Figure JPOXMLDOC01-appb-C000003
Wherein, R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkoxyalkyl group of the alkyl group or a C 2-8 1-8 carbon atoms. ]

Specific compounds represented by the general formula (1), (meth) acrylate, (meth) acrylate, (meth) acrylic acid n- propyl, isopropyl (meth) acrylate, (meth) acrylic acid n- butyl, isobutyl (meth) acrylate, butyl (meth) tert- acrylate, (meth) amyl acrylate, (meth) acrylic acid n- hexyl, (meth) acrylic acid n- octyl, and (meth) acrylic having an alkyl group having 1-8 carbon atoms, 2-ethylhexyl, etc. (meth) acrylic acid alkyl ester compound; (meth) acrylic acid methoxymethyl, (meth) acrylic acid ethoxymethyl, (meth) acrylic acid butoxymethyl, ( meth) methoxyethyl acrylate, ethoxyethyl (meth) acrylate, (meth) butoxyethyl acrylate (Meth) methoxybutyl acrylate, and (meth) ethoxy butyl acrylate and (meth) having an alkoxyalkyl group having 2-8 carbon atoms such as butoxybutyl acrylic acid (meth) acrylic acid alkoxyalkyl compounds. These compounds may be used alone or may be used in combination of two or more.
Ratio of the second compound represented by the general formula relative to the total amount of the monomer component (1) is preferably at least 50 mol%, more preferably at least 80 mol%, it is 95 mol% or more but more preferable.

The second monomer component, in addition to the compound represented by the general formula (1), this can be used and other copolymerizable monomers. The copolymerizable monomer such as (meth) acrylic acid, itaconic acid, maleic acid, alpha and fumaric acid, beta-ethylenically unsaturated carboxylic acid monomers; (meth) acrylate n- nonyl, (meth) acrylate, isononyl (meth) acrylate, decyl (meth) having an alkyl group having 9 or more carbon atoms of dodecyl acrylate (meth) acrylic acid alkyl ester compound; styrene, alpha-methyl styrene, vinyl toluene, and the like vinyl aromatic monomers; (meth) acrylate, cyclohexyl (meth) acrylate cyclohexyl, (meth) acrylic acid t- butyl cyclohexyl (meth) acrylic acid cyclododecyl, (meth) acrylate and isobornyl alicyclic vinyl monomers; 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 3-hydrate Kishipuropiru, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and polyethylene - hydroxyl group-containing monomers such as polypropylene glycol mono (meth) acrylate; acrylamides, (meth) acrylonitrile, vinyl acetate and the like, can be used one or two or more of them.

The second monomer component may contain a crosslinkable monomer. Examples of the crosslinkable monomer, it is possible to use the same monomers as those described in the first step. As described above, when using a crosslinkable monomer in the second step can be obtained an elastomer having an interpenetrating network structure, if you do not use the crosslinkable monomer is a semi-interpenetrating elastomer having a network structure is obtained. In either form in which the effects of the present invention.

The amount of the crosslinkable monomer in the second monomer component, of the nonionic vinyl monomer used type, but may vary depending on the resulting elastomer applications, the crosslinking monomer preferably the second is 0 ~ 2 mol% based on the total amount of monomer components excluding, more preferably 0.001 ~ 1.0 mol%, it is 0.005 ~ 0.5 mol% more preferably, and most preferably 0.01 ~ 0.1 mol%. The amount of the crosslinkable monomer can be obtained a good elastomeric flexibility equal to or less than 2 mol%.

In the present invention, the glass transition temperature of the second derived from a monomer polymer (Tg) of in the range of -80 ~ 20 ° C., preferably in the range of -70 ~ 10 ° C., more preferably - it is in the range of 60 ~ 0 ℃. Since Tg is is too hard polymer obtained exceeds 20 ° C., may not be suitable for use as an elastomer. Moreover, the restriction or the like of the raw material monomer, generally a Tg not fall below -80 ° C..

In the present invention, the value of Tg of the second derived from a monomer polymer obtained by a result of the DSC measurement. In this case, the measurement of DSC, in nitrogen atmosphere, carried out at a heating rate 10 ° C. / min conditions.

Also, the type and amount of the monomer components above the Tg except crosslinkable monomer, for example, "POLYMER HANDBOOK-Fourth Edition" (John Wiley & Sons, Inc. Issuance) of each homopolymer listed in based on the tg, it may be used a value determined by calculation as shown in formula (1).
1 / Tg = {W (a) / Tg (a)} + {W (b) / Tg (b)}
+ {W (c) / Tg (c)} + ··· (1)
In the above formulas,
Tg: Tg of the polymer
W (a): the weight fraction W of the structural unit consisting of the monomer (a) in the polymer (b): the weight fraction W of the structural unit consisting of the monomer (b) in the polymer (c): Weight weight fraction Tg of the structural unit consisting of the monomer (c) in the polymer (a): homopolymer glass transition temperature Tg of the monomer (a) (b): a homopolymer of the monomer (b) the glass transition temperature Tg of (c): a glass transition temperature of the homopolymer of the monomer (c)

As described above, in the second step polymerization after blending polymer and the second monomer component obtained by the first step, the second monomer component is introduced into the first network structure, or carry out the polymerization and crosslinking. Polymerizing a second monomer component, or polymerization, and a method of crosslinking can be carried out by the same method as the first step.
Further, in the second step, it is possible to use a solvent selected from water or various organic solvents, in that the second monomer component can be efficiently introduced into the first network structure, the solvent it is preferable not to use. In this case, a polymer obtained by the first step, it is preferred from the viewpoint of the operation used in the polymer itself is cut or crushed to a suitable size.

In the second step, a second monomer component is absorbed by the polymer obtained by the first step, it is preferable to carry out the polymerization after being fully introduced into the first network structure. Therefore, after mixing the polymer obtained by the first step a second monomer component, it may be subjected to a treatment of heating, if necessary. Warming, for example raised to about 30 ~ 80 ° C., can be carried out keeping in mind the volatilization of such monomers or solvents used. Also, after mixing the second monomer, in order to sufficiently absorb the polymer obtained by the first step, the electrostatic 置又 preferably more than 1 minute under stirring, more preferably after more than 1 hour the it is preferred to initiate the polymerization of two steps.

In the present invention, it is necessary that the weight ratio of the first monomer component and the second monomer component is in the range of 1 / 0.1 to 1/30. A preferred range of the mass ratio is 1 / 1-1 / 10, and more preferred range is 1 / 2-1 / 8. When the ratio of the amount of the second monomer component to the first monomer component is less than 0.1, there may be poor in flexibility of the elastomer. Also, if the proportion exceeds 30, the amount of first network structure is not sufficient (semi) interpenetrating network structure for relatively small is formed, the strength of the elastomer which satisfies there is no fear that obtained .

Elastomers of the present invention, the first step and is obtained through a method described in the second step, a plasticizer, oil, antioxidant, inorganic fillers, pigments, antioxidants and ultraviolet absorbers it may be used by blending known additives. It is also possible to mix addition of other elastomers.

Hereinafter, the present invention will be specifically described based on Examples. The present invention is not limited by these examples. Incidentally, "parts" and "%" in the following are parts by mass and mass% unless otherwise specified.

Example 1
(First step)
As a first monomer component, ethyl acrylate (hereinafter "EA" hereinafter) and 1,4-butanediol diacrylate (hereinafter, referred to as "1,4BDA") ratio of 100 / 0.02 in molar ratio in were mixed. Then, as the photopolymerization initiator 2,2-dimethoxy-1,2-diphenylethane-1-one (BASF's trade name "Irgacure651") at a rate of 100 / 0.02 in molar ratio with respect to EA a first monomer liquid was prepared by adding and mixing. Between two glass plates of 1mm thick sealing the periphery with a silicone rubber having a thickness of 0.5mm pouring a first monomer liquid, irradiation with ultraviolet rays at an illuminance of 0.9 mW / cm 2 by using a black light It was started. After 30 minutes, to confirm that the polymerization by IR was complete to give a polymer A1 having a first network structure.
(Second step)
The EA and Irgacure651 were mixed at a ratio of 100 / 0.02 in molar ratio to prepare a second monomer liquid. The polymer A1 was cut to a size of 30mm × 80mm × 0.5mm, immersed in a sufficient amount of the second monomer liquid. By 4 hours to stand at room temperature in this state, it was sufficiently swell the second monomer component in the polymer A1. The second polymer A1 was sufficiently swelled by the monomer component extraction, after wiping lightly monomers body fluid attached to the periphery of the polymer, the by measuring the difference in weight of the polymer A1 in the before and after swelling was calculated swelling capacity due to second monomer liquid, a value of 8.3 times as swelling capacity was obtained.
Sandwiched between a glass plate of the second polyethylene terephthalate release film and the thickness of 1mm thickness 50μm the polymer A1 swollen with monomer liquid, UV at an illuminance of 0.9 mW / cm 2 by using a black light It was the start of the irradiation. After 30 minutes, to confirm that the polymerization by IR was complete, to give an elastomer A1 having a semi-interpenetrating network structure. The composition of the elastomeric A1 calculated from the charged amounts was the proportion of EA / 1,4BDA = 100 / 0.0024 (molar ratio).
The resulting elastomer A1 to prepare a test piece punched out in 6 dumbbell was subjected to a tensile test. Tensile test in compliance with JIS-K6251, the tensile strength at break of the test piece, the tensile elongation at break and 50% modulus was measured and the results are shown in Table 2.

Examples 2-7
In a first monomer liquid, the elastomer A2 ~ A7 have a semi-interpenetrating network structure in the same manner as in Example 1 except that charge of EA / 1,4BDA (molar ratio) was changed as shown in Table 1 Obtained. The results of the tensile tests performed on these are shown in Table 2.

Comparative Example 1
Charge of monomer (molar ratio) to give the EA / 1,4BDA = 100 / 0.0024 elastomer C1 by the performing the same operation as the first step of Example 1 was changed to. Although elastomer C1 is identical composition charged monomers as a whole elastomer A1 and elastomer obtained in Example 1, since the elastomer obtained from only the first step, the (semi) interpenetrating network structure it is those which do not have. The results of the tensile tests performed on the elastomer C1 shown in Table 2.

Comparative Example 2 to 4
Except that the charging ratio of monomers were changed as shown in Table 1, to obtain an elastomer C2 ~ C4 without a (semi) interpenetrating network structure in the same manner as in Comparative Example 1. The results of the tensile tests performed on these are shown in Table 2.

Comparative Example 5
First as a single monomer component, EA, ionic monomer having a structure represented by formula (2) (hereinafter, referred to as "monomer A") to and 1,4BDA in a molar ratio of 80/20/0 were mixed with .20 ratio, then semi-interpenetrating network in the same manner as in example 1 except that the addition at a ratio of 100 / 0.02 in molar ratio with respect to the total of the Irgacure 651 EA and monomer a to give an elastomer C5 having the structure. The results of the tensile tests performed on the elastomer C5 shown in Table 2.

Figure JPOXMLDOC01-appb-C000004

Figure JPOXMLDOC01-appb-T000005

Figure JPOXMLDOC01-appb-T000006

Examples 8 to 15
Except that the composition of the first monomer component and the second monomer components were changed as shown in Table 3, the elastomer B8 ~ B15 having a (semi) interpenetrating network structure in the same manner as in Example 1 It was obtained. The results of the tensile tests performed on these are shown in Table 4.

Figure JPOXMLDOC01-appb-T000007

Figure JPOXMLDOC01-appb-T000008

Table 1 and of the compounds used in Table 3 details below.
EA: Ethyl acrylate BA: butyl acrylate 1,4BDA: 1,4- butanediol

(Repeated tensile test)
For each elastomer obtained in Example 4, 9, and Comparative Example 5, after pulling the specimen before rupture under the same conditions as the tensile test was repeated 3 cycles operation for opening the stress. The results are shown in Figures 1-3.

Examples 1-15 are all elastomer belonging to the present invention. Among them, Examples 1 to 7, 12 and 14 are elastomers having a semi-interpenetrating network structure, Examples 8 to 11, 13 and 15 is an elastomer having an interpenetrating network structure. Elastomer obtained in each example were both show a sufficiently high tensile strength.
Further, as shown in FIG. 1 and 2, the elastomer of the present invention is not observed little hysteresis loss in repeated tensile test results but also excellent in durability was shown.

On the other hand, Comparative Examples 1-4, an elastomer having no (semi) interpenetrating network structure. These are the composition of the entire elastomer despite having the same monomer composition as in Examples 1-4, the tensile strength was as 0.26 ~ 0.43 MPa and low. Comparative Example 5 is an elastomer having a semi-interpenetrating network structure, is intended to include ionic monomers in the first monomer component. Its tensile strength at break showed good values, it was confirmed that produce large hysteresis loss in repeated tensile test measured for Comparative Example 5 (Fig. 3).

Elastomers of the present invention, exhibit excellent strength, hardly hysteresis loss due to tensile stress. Therefore, not only the sealing material or packing material such only, automobile tires material, as well, such as building materials and medical materials, etc., applications are expected for applications such as high strength and high durability are required.

Claims (4)

  1. After forming the first network structure by polymerization and crosslinking a first monomer component, introducing a second monomer component into the network structure in said first polymerization or polymerization and crosslinking a elastomer having obtained (semi) interpenetrating network structure by,
    The first monomer component consists only nonionic vinyl monomer,
    It said second glass transition temperature of the polymer obtained from monomer component (Tg) is the -80 ~ 20 ° C.,
    The mass ratio of the first monomer component and the second monomer component, 1 / 0.1 to 1/30 the elastomer is.
  2. Wherein the first monomer component, elastomer according to claim 1 for use 0.01 ~ 2 mol% of crosslinking monomer based on the total amount of the monomers except for the crosslinking monomer.
  3. Wherein the second monomer component, elastomer according to claim 1 or 2 using 0 ~ 2 mol% of crosslinking monomer based on the total amount of the monomers except for the crosslinking monomer.
  4. The second monomer component, elastomer according to any one of claims 1 to 3, containing a compound represented by the following general formula (1) or 80 mol%.
    Figure JPOXMLDOC01-appb-C000001
    Wherein, R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkoxyalkyl group of the alkyl group or a C 2-8 1-8 carbon atoms. ]
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63291909A (en) * 1987-05-26 1988-11-29 Mitsubishi Petrochem Co Ltd Production of water absorbing composite material
JPH07324174A (en) * 1994-05-31 1995-12-12 Dainippon Ink & Chem Inc Nonaqueous colored resin dispersion and its production
JPH11158343A (en) * 1997-11-26 1999-06-15 Nok Corp Production of (meth)acrylic polymer blend composition
JP2007502878A (en) * 2003-08-20 2007-02-15 ビーエーエスエフ アクチェンゲゼルシャフトBASF Aktiengesellschaft Molding material
JP2011038021A (en) * 2009-08-14 2011-02-24 Fujimori Kogyo Co Ltd Method for manufacturing adhesive composition, method for manufacturing adhesive film, raw material composition for adhesive agent, and adhesive film
JP2011527377A (en) * 2008-07-07 2011-10-27 バイオミメディカ インコーポレイテッド Hydrophilic interpenetrating polymer network derived from a hydrophobic polymer
JP2012036262A (en) * 2010-08-04 2012-02-23 Hokkaido Univ Polymer gel and method for producing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63291909A (en) * 1987-05-26 1988-11-29 Mitsubishi Petrochem Co Ltd Production of water absorbing composite material
JPH07324174A (en) * 1994-05-31 1995-12-12 Dainippon Ink & Chem Inc Nonaqueous colored resin dispersion and its production
JPH11158343A (en) * 1997-11-26 1999-06-15 Nok Corp Production of (meth)acrylic polymer blend composition
JP2007502878A (en) * 2003-08-20 2007-02-15 ビーエーエスエフ アクチェンゲゼルシャフトBASF Aktiengesellschaft Molding material
JP2011527377A (en) * 2008-07-07 2011-10-27 バイオミメディカ インコーポレイテッド Hydrophilic interpenetrating polymer network derived from a hydrophobic polymer
JP2011038021A (en) * 2009-08-14 2011-02-24 Fujimori Kogyo Co Ltd Method for manufacturing adhesive composition, method for manufacturing adhesive film, raw material composition for adhesive agent, and adhesive film
JP2012036262A (en) * 2010-08-04 2012-02-23 Hokkaido Univ Polymer gel and method for producing the same

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