JP2010241961A - (meth)acrylic curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for further improving physical properties of a cured product of a curable composition comprising a (meth)acrylic polymer having a reactive functional group at its end. <P>SOLUTION: The curable composition includes: a (meth)acrylic block polymer (A); and a (meth)acrylic polymer (B) having a reactive functional group at least one of its ends. The physical properties such as strength of the cured product can be improved by blending the (meth)acrylic block polymer (A) that is highly compatible with the (meth)acrylic polymer (B). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a (meth) acrylic curable composition for providing a cured product having excellent heat resistance and flexibility and further improved physical properties such as strength.

  It is known that a polymer having at least one reactive functional group at a molecular terminal is crosslinked under appropriate conditions to obtain a rubber-like cured product.

  For example, when the reactive functional group is a reactive silicon group, it is crosslinked even at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture or the like. Polymers whose main chain skeleton is a polyoxyalkylene polymer or a polyisobutylene polymer have already been industrially produced and are widely used for applications such as sealing materials, adhesives, and paints (Patent Documents 1 and 2). Such). In addition, many reports have been made on curable compositions whose main chain skeleton is made of a vinyl polymer such as a (meth) acrylic polymer (Patent Document 3, etc.). Furthermore, many reports have been made on curable compositions comprising a polymer whose main chain skeleton is polysiloxane (Patent Document 4, etc.).

  A polymer having an alkenyl group as a reactive functional group is also used as the curable composition. It is known to use a compound having a hydrosilyl group as a curing agent to give a cured product excellent in quick curing, deep curing, and mechanical properties (Patent Documents 5 to 7, etc.). As the main chain skeleton of such a polymer having an alkenyl group, various polymers are known. Polyether polymers such as polyethylene oxide, polypropylene oxide, polytetramethylene oxide; polybutadiene, polyisoprene, poly Examples include hydrocarbon polymers such as chloroprene, polyisobutylene, and hydrogenated products thereof; polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, and polycaprolactone; and silicone polymers such as polydimethylsiloxane.

  Furthermore, a polymer having a reactive functional group having a polymerizable double bond is also used as a curable composition, and can be rapidly cured by active energy rays such as ultraviolet rays or heat (Patent Documents 8 and 9, etc.).

  On the other hand, when focusing on the polymer main chain, curing using a polymer whose main chain is a (meth) acrylic polymer due to the diversity of structure, ease of design, and excellent heat resistance and weather resistance of the cured product. Sexual compositions have been vigorously developed in recent years (Patent Documents 3, 7, 8, 9, etc.).

JP-A-52-73998 JP-A 63-6041 JP-A-11-130931 Japanese Patent Laid-Open No. 55-43119 JP-A-3-181565 International Publication WO 96/15194 JP-A-11-080570 JP 2000-72816 A JP 2000-95826 A

  The subject of this invention is providing the method for further improving the physical property of hardened | cured material in the curable composition which consists of a (meth) acrylic-type polymer which has a reactive functional group at the terminal.

  As a result of intensive studies by the present inventors in view of the above-described present situation, a (meth) acrylic block copolymer is used for a curable composition comprising a (meth) acrylic polymer having a reactive functional group at the terminal. As a result, it was found that the physical properties such as the strength of the cured product can be improved by adding, and the present invention has been completed.

That is, the present invention includes the following two components;
(A): (a) (meth) acrylic polymer block and (b) (meth) acrylic block copolymer containing acrylic polymer block,
(B): It relates to a curable composition comprising a (meth) acrylic polymer having a reactive functional group at at least one terminal.

  In the present invention, the terminal reactive functional group of the (meth) acrylic polymer (B) is a reactive silicon group, an alkenyl group, a polymerizable double bond group, a hydroxyl group, a carboxyl group, an epoxy group, or an amino group. The present invention relates to a curable composition which is at least one group selected from the group consisting of:

  Moreover, this invention relates to the curable composition whose number average molecular weight (Mn) of a (meth) acrylic-type polymer (B) is 1000-200000.

  In the present invention, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography of the (meth) acrylic polymer (B) is 1.8 or less. It relates to a curable composition.

  The present invention also relates to a curable composition in which the main chain of the (meth) acrylic polymer (B) is composed of an acrylate ester.

  In the present invention, the (meth) acrylic block copolymer (A) is a (a)-(b)-(a) triblock copolymer or (a)-(b) diblock copolymer. It relates to a curable composition.

  Moreover, this invention relates to the curable composition whose number average molecular weight (Mn) of a (meth) acrylic-type block copolymer (A) is 10000-500000.

  In the present invention, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography of the (meth) acrylic block copolymer (A) is 1.8. The following relates to the curable composition.

  In the present invention, the (meth) acrylic block copolymer (A) is composed of (a) (meth) acrylic polymer block of 5 to 90% by weight and (b) acrylic polymer block of 95 to 10% by weight. It relates to a curable composition which is a block copolymer.

  Moreover, this invention is the monomer unit which comprises either (a) (meth) acrylic-type polymer block or (b) acrylic-type polymer block in (meth) acrylic-type block copolymer (A). It relates to a curable composition in which 50% by weight or more is the same as the monomer unit constituting the (meth) acrylic polymer (B).

  In the present invention, the (meth) acrylic block copolymer (A) further includes a reactive silicon group, an alkenyl group, a polymerizable double bond group, a halogen group, a hydroxyl group, a carboxyl group, an acid anhydride group, The present invention relates to a curable composition which is a block polymer having at least one group selected from the group consisting of an epoxy group and an amino group.

  In the present invention, the blend ratio of the (meth) acrylic polymer (B) to the (meth) acrylic block copolymer (A) is 100 parts by weight of the (meth) acrylic polymer (B). The (meth) acrylic block copolymer (A) relates to a curable composition having 1 to 500 parts by weight.

  The (meth) acrylic polymer (B) having a reactive functional group at at least one terminal is blended with a compatible (meth) acrylic block polymer (A) to form a curable composition. Thus, physical properties such as strength of the cured product are improved.

The curable composition comprising the (meth) acrylic block copolymer (A) of the present invention and the (meth) acrylic polymer (B) having a reactive functional group at least at one end. This will be described in detail.
<< Main chain of (meth) acrylic polymer (B) >>
The (meth) acrylic monomer constituting the main chain of the (meth) acrylic polymer (B) having a reactive functional group at at least one end of the present invention is not particularly limited, and various types can be used. it can. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (meth) acrylic acid-t-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid lauryl, (meth) Myristyl acrylate, palmitic acid (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, (meth) a Toluyl toluate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid-3-ethoxypropyl, (meth) acrylic acid-4-ethoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-3-hydroxypropyl, (Meth) acrylic acid glycidyl, (meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethylmethyl, (meta ) 2-Trifluoromethylethyl acrylate, 2-perfluoro (meth) acrylate Roethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate , (Meth) acrylic acid 2-perfluoromethyl-2-perfluoroethylmethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic acid 2- Examples include (meth) acrylic acid ester monomers such as perfluorohexadecylethyl.

  In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  These (meth) acrylic monomers may be used alone or a plurality of them may be copolymerized. These (meth) acrylic monomers may be copolymerized with other vinyl monomers, but the (meth) acrylic monomers are preferably contained in a weight ratio of 60% or more, and more than 70%. More preferably, it is contained 80% or more, more preferably 90% or more.

  Other vinyl monomers copolymerized with (meth) acrylic monomers include styrene monomers (aromatic vinyl monomers) such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid salts; Fluorine-containing vinyl monomers such as fluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; monoalkyl and dialkyl esters of maleic acid; monoalkyl esters of fumaric acid And dialkyl esters; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmer Maleimide monomers such as imide and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, benzoic acid Examples thereof include vinyl esters such as vinyl and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

  The main chain structure of the (meth) acrylic polymer (B) of the present invention is not particularly limited, but may be linear or branched. A polymer having a plurality of branch points, that is, a so-called star polymer is also included in the (meth) acrylic polymer (B) of the present invention.

  The number average molecular weight (Mn) of the (meth) acrylic polymer (B) of the present invention is not particularly limited, but is preferably in the range of 1000 to 200000, more preferably in the range of 3000 to 150,000, and in the range of 5000 to 100,000. More preferably, 7000-50000 is particularly preferable. The molecular weight distribution of the (meth) acrylic polymer (B), that is, the ratio (Mw / Mn) of the weight average molecular weight (Mn) and the number average molecular weight (Mw) measured by gel permeation chromatography (GPC) is Although it does not specifically limit, Preferably it is less than 1.8, Preferably it is less than 1.7, More preferably, it is less than 1.5, More preferably, it is less than 1.3. A narrow molecular weight distribution, that is, a small Mw / Mn value means that there is little variation in the length of the molecules. In the GPC measurement of the present invention, chloroform is usually used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The vinyl polymer main chain obtained by the production method of the present invention may be linear or branched.

≪Terminal reactive functional group of (meth) acrylic polymer (B) ≫
The (meth) acrylic polymer (B) of the present invention has a reactive functional group at at least one molecular terminal. The reactive functional group is not particularly limited, and examples thereof include a reactive silicon group, an alkenyl group, a polymerizable double bond group, a halogen group, a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, and an amino group. .

Although it does not specifically limit as a reactive silicon group used as the terminal functional group of a (meth) acrylic-type polymer (B), The thing represented by General formula (1) is used suitably.
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
{Wherein, R ^1, R ² represents an alkyl group containing 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or _{^{(R 3), 3 SiO- (}} R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ³ may be the same or different, and represents a triorganosiloxy group represented by R ¹ or When two or more R ² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. }
The group represented by these is mentioned.

  Examples of the hydrolyzable group include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling. Among alkoxy groups, those having fewer carbon atoms have higher reactivity, and the reactivity decreases in the order of methoxy group> ethoxy group> propoxy group, and can be selected according to the purpose and application.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (a + Σb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silyl group, they may be the same or different. The number of silicon atoms forming the crosslinkable silyl group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less. In particular, the general formula (2)
-Si (R ² ) _3-a (Y) _a (2)
A crosslinkable silyl group represented by the formula (wherein R ² and Y are the same as described above, and a is an integer of 1 to 3) is preferable because it is easily available.

  Although there is no particular limitation, for example, when Y is the same, the reactivity of Y increases as a increases, so the curability and mechanical properties of the cured product can be controlled by variously selecting Y and a. Can be selected according to the purpose and application.

  Those having a of 1 are mixed with a polymer having a crosslinkable silyl group as a chain extender, specifically, at least one polymer comprising polysiloxane, polyoxypropylene, polyisobutylene, and polyacryl. Can be used. It is possible to obtain a composition having low viscosity before curing, high elongation at break after curing, low bleeding, low surface contamination, and excellent paint adhesion.

  When a is 2 or more, a curable composition excellent in curability, weather resistance after curing, adhesive strength, strength at break, tear strength and the like can be obtained. In addition, stickiness (surface tack) is suppressed while lowering the crosslink density in order to obtain flexibility after curing, especially when extremely fast curing speeds are required, such as for adhesive applications and at low temperatures. When it is desired to do so, it is preferable that a is 3 (for example, trimethoxy functional group). Although those having a of 3 (for example, trimethoxy functional group) cure faster than those having 2 (for example, dimethoxy functional group), those having 2 are superior in terms of storage stability and mechanical properties (elongation, etc.). There is a case. In order to balance the curability and physical properties, two (for example, dimethoxy functional group) and three (for example, trimethoxy functional group) may be used in combination.

  Although it does not specifically limit as an alkenyl group used as the terminal functional group of a (meth) acrylic-type polymer (B), The thing represented by General formula (3) is used suitably.

（式中、Ｒ⁴は、水素原子あるいは炭素数１〜２０の炭化水素基を示す。Ｒ⁵は炭素数１〜２０のアルキレン基、または、エーテル結合、エステル結合、アミド結合、ウレタン結合からなる群より選ばれる１種の基を示す。Ｒ⁶は水素原子あるいは炭素数１〜２０の炭化水素基を示し、複数のＲ⁶は同じでも異なってもよい。ｎは０〜１０の整数。）
Ｒ⁶は水素原子またはメチル基が好ましい。また、これらの中でも特に一般式（４）の構造が好ましい。

(In the formula, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ⁵ is an alkylene group having 1 to 20 carbon atoms, or an ether bond, an ester bond, an amide bond, or a urethane bond. One group selected from the group, R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ⁶ may be the same or different, and n is an integer of 0 to 10.)
R ⁶ is preferably a hydrogen atom or a methyl group. Of these, the structure of the general formula (4) is particularly preferable.

（式中、Ｒ⁴は、水素原子あるいは炭素数１〜２０の炭化水素基を示す。ｐは１〜２０の整数。）
さらに、Ｒ⁴は水素原子またはメチル基が好ましい。

(In the formula, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. P is an integer of 1 to 20)
R ⁴ is preferably a hydrogen atom or a methyl group.

  (B) Although it does not specifically limit as a polymerizable double bond group used as the terminal functional group of a (meth) acrylic-type polymer, The structure of General formula (5) or General formula (6) is preferable.

（式中、Ｒ⁷は水素、または、炭素数１〜２０の炭化水素基を表す。Ａｒは置換基を有していてもよい炭素数６〜２０の２価の芳香環を表す。）
Ｒ⁷は水素またはメチル基が好ましい。重合性の二重結合基としては、これらの中でも特に（メタ）アクリロイルオキシ基が好ましい。

(Wherein R ⁷ represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Ar represents a divalent aromatic ring having 6 to 20 carbon atoms which may have a substituent.)
R ⁷ is preferably hydrogen or a methyl group. Of these, a (meth) acryloyloxy group is particularly preferable as the polymerizable double bond group.

  Although it does not specifically limit as a halogen group used as the terminal functional group of a (meth) acrylic-type polymer (B), A fluorine, chlorine, bromine, and iodine are preferable.

  The (meth) acrylic polymer (B) used in the present invention is characterized by having a reactive functional group at at least one molecular terminal. By arranging the reactive functional group at the terminal, for example, the molecular weight between cross-linking points of the cured product can be increased, and as a result, physical properties such as flexibility and high elongation of the cured product are expressed.

  In the present invention, the polymer (B) having a reactive functional group at at least one molecular terminal is a mixture with a polymer in which a functional group is not introduced at the terminal, as a by-product in the production process. However, it is preferable that a functional group is surely introduced for the expression of physical properties, and specifically, the above-mentioned reactive functional group has an average of 0.1 per molecule of the (meth) acrylic polymer (B). Preferably, 5 or more are included, more preferably 0.6 or more, more preferably 0.7 or more, and more preferably 0.8 or more. Particularly preferred.

  In the composition of the present invention, it is possible to control the curability and the mechanical properties of the cured product by the number of reactive functional groups of the (meth) acrylic polymer (B), depending on the purpose and application. You can choose. When the (meth) acrylic polymer (B) has a function as a chain extender or a reactive diluent, the reactive functional group described above per molecule of the (meth) acrylic polymer (B) It is preferable that an average of 0.5 to 1.5 is included, more preferably 0.6 to 1.4, and more preferably 0.7 to 1.3 or more. Preferably, 0.8 to 1.2 are included. On the other hand, when the (meth) acrylic polymer (B) is used as a main agent or when it has a function as a crosslinking agent, the reactive functional group is a molecule of the (meth) acrylic polymer (B). It is preferable that an average of 1.5 to 2.5 is included, more preferably 1.6 to 2.4, and more preferably 1.7 to 2.3 or more. More preferably, it is particularly preferably 1.8 to 2.2. There is no particular upper limit to the number of reactive functional groups in the (meth) acrylic polymer (B), and if it is desired to give special effects such as high strength and rapid curing, 2.5 or more per molecule. A thing can also be used suitably. In this case, as described above, the (meth) acrylic polymer (B) may be branched in the main chain, and may be a so-called star polymer.

<< Main chain structure of (meth) acrylic block copolymer (A) >>
The curable composition comprising the (meth) acrylic polymer (B) having a reactive functional group at at least one molecular terminal may be, for example, a filler, a plasticizer, an anti-aging agent, or a pigment as necessary. In addition, physical properties can be prepared by blending additives such as an adhesion-imparting agent, a stabilizer, and a solvent. In order to improve physical properties such as breaking strength, breaking elongation, adhesion to various adherends, and weather resistance adhesion of the cured product, for example, Japanese Patent Application Laid-Open Nos. 2001-279108, 2004-083865, and 2005. Although it is effective to add various fillers as disclosed in JP-A-3320519, the present invention is characterized by using a thermoplastic elastomer.

  Generally, a thermoplastic elastomer is an alloy composed of a rubber component (soft segment) that exhibits entropy elasticity and a constraining component (hard segment) that flows at a high temperature but prevents plastic deformation at a normal temperature and gives the rubber component a reinforcing effect. Taking the structure. For example, in a styrene-based elastomer, styrene blocks aggregate to serve as hard segments, and butadiene-based blocks or isoprene-based blocks serve as a matrix and serve as soft segments. In addition, the olefin elastomer has an alloy structure in which rubber such as EPDM is dispersed in a resin such as PP. In any case, thermoplastic processing such as injection molding is possible because the hard segment flows at a high temperature. Examples of the thermoplastic elastomer include vinyl chloride elastomers, ester elastomers, amide elastomers, urethane elastomers, etc., in addition to styrene elastomers and olefin elastomers.

  Furthermore, it is known that a (meth) acrylic block copolymer having methyl methacrylate or the like as a hard segment and butyl acrylate or the like as a soft segment can also be used as a thermoplastic elastomer. As a block copolymer containing a (meth) acrylic polymer block and an acrylic polymer block, polymethyl methacrylate-b-polybutyl acrylate-b-polymethacrylic acid disclosed in Patent Registration No. 2553134 Block copolymer of methyl (PMMA-b-PBA-b-PMMA), polymethyl methacrylate-b-polyethyl acrylate 2-ethylhexyl-b-polymethyl methacrylate (PMMA-b-P (2EHA ) -B-PMMA). The (meth) acrylic block copolymer is characterized by excellent weather resistance, durability, heat resistance and oil resistance. Further, various studies have been made as disclosed in JP 2004-315608 A, JP 2003-277574 A, and the like. The (a) (meth) acrylic polymer block and the (b) (meth) acrylic block copolymer (A) containing the acrylic polymer block used in the present invention are not particularly limited. A thing can be used suitably.

  The structure of the (meth) acrylic block copolymer (A) of the present invention is at least one selected from a linear block copolymer (A1) or a branched (star) block copolymer (A2). The (meth) acrylic block copolymer (A) is preferably used.

  The linear block copolymer (A1) may have any structure, but contains a diblock copolymer, a triblock copolymer, or both from the viewpoint of physical properties of the composition. It is preferable that these block copolymers are the main component. Examples of the structure of the block copolymer other than the diblock copolymer and the triblock copolymer include a multiblock copolymer. Examples of the structure of the (meth) acrylic block copolymer (A) of the present invention include a diblock copolymer, a triblock copolymer, a mixture of a triblock copolymer and a diblock copolymer, a triblock copolymer, A mixture of a block copolymer and a multiblock copolymer, or a mixture of a diblock copolymer, a triblock copolymer, and a multiblock copolymer is more preferable, and among them, a diblock copolymer and a triblock copolymer are preferable. More preferably, the main component is a block copolymer.

In these cases, the (meth) acrylic polymer block is expressed as a, the acrylic polymer block is expressed as b, the diblock copolymer is ab type, and the triblock copolymer is ab. a -a type or b-a-b-type, multi-block copolymers as is an integer of 1 or more and _{n a- (b-a) n} -b -type, a-b- (a-b ) n -a Type, b- (ab) _n -ab type. Among these, from the viewpoint of impact resistance, the triblock copolymer is preferably an aba type, and the multiblock copolymer is an a- (ba) _n- b type or an ab- (A-b) _n- a type is preferable. Further, from the viewpoint of moldability, an aba type triblock copolymer, a multiblock copolymer, or a mixture thereof is preferable, and an aba type triblock copolymer is more preferable. preferable.

  The branched (star-shaped) block copolymer (A2) may have any structure, but from the viewpoint of the physical properties of the composition, the block copolymer having the linear block copolymer as a basic unit. It is a polymer.

  The structure of such a block copolymer is properly used according to the required properties such as moldability, processing characteristics, mechanical properties, and applications.

  The (meth) acrylic block copolymer (A) in the present invention is within the scope of the present invention even if it contains a homopolyacrylic acid ester, a homopolymethacrylic acid ester and the like by-produced in the production process. However, in order to develop physical properties, it is preferable that the number of these homopolymers is small. Specifically, the (meth) acrylic block copolymer (A) contains an average of 60% by weight or more of molecules having a block structure. Preferably, it is contained at 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

  The number average molecular weight (Mn) of the (meth) acrylic block copolymer (A) used in the present invention is not particularly limited, and the (meth) acrylic polymer block (a) and the acrylic polymer block (b) ) May be determined from the molecular weight required for each. When the range of the number average molecular weight of a block copolymer (A) is illustrated, when mainly aiming at the impact resistance modification, 30000-500000 are preferable, 40000-400000 are more preferable, and 50000-300000 are further. preferable. Moreover, when mainly aiming at the improvement of workability, 10000-1 million are preferable, 20000-700000 are more preferable, and 30000-400000 are further more preferable. Moreover, when aiming at obtaining the compound material which has the elasticity modulus between resin and an elastomer, 10000-500000 are preferable, 30000-400000 are more preferable, 50000-300000 are further more preferable. In these cases, if the number average molecular weight is small, the physical properties may deteriorate, and sufficient mechanical properties as an elastomer may not be expressed. If the number average molecular weight is large, the viscosity tends to increase and the workability tends to decrease. Therefore, it is set according to the required physical property balance.

  The molecular weight distribution of the (meth) acrylic block copolymer (A), that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography is not particularly limited. However, it is preferably less than 1.8, preferably less than 1.7, and more preferably less than 1.5. A narrow molecular weight distribution, that is, a small Mw / Mn value means that there is little variation in the length of the molecules. When Mw / Mn exceeds 1.8, the uniformity of the (meth) acrylic block copolymer (A) tends to decrease.

  The composition ratio of the (meth) acrylic polymer block (a) and the acrylic polymer block (b) constituting the (meth) acrylic block copolymer (A) is not particularly limited, and is required in the use application. What is necessary is just to determine from the physical weight to be processed, the moldability requested | required at the time of a process of a composition, and the molecular weight each required for a (meth) acrylic-type polymer block (a) and an acrylic-type polymer block (b).

  When the range of the composition ratio of the (meth) acrylic polymer block (a) and the acrylic polymer block (b) is exemplified, the (meth) acrylic polymer block (a) is 5 to 95% by weight, the acrylic heavy The combined block (b) is preferably 95 to 5% by weight. More preferably, it is 5 to 50% by weight, and the acrylic polymer block (b) is 95 to 50% by weight. More preferably, the (meth) acrylic polymer block (a) is 10 to 40% by weight and acrylic. The polymer block (b) is 90 to 60% by weight. If the proportion of the (meth) acrylic polymer block (a) is less than 10% by weight, the rubber elasticity at high temperature tends to be reduced, and if it is more than 40% by weight, the mechanical properties as an elastomer, particularly fracture. Elongation tends to decrease.

The relationship between the glass transition temperatures of the (meth) acrylic polymer block (a) and the acrylic polymer block (b) constituting the (meth) acrylic block copolymer (A) is the (meth) acrylic polymer. the glass transition temperature of the block _(a) Tg a, as it Tg _b of the acrylic polymer block (b), it is preferable to satisfy the relation of the following equation.

Tg _a > Tg _b
The setting of the glass transition temperature (Tg) of the polymer (meth) acrylic polymer block (a) and the acrylic polymer block (b) is roughly in accordance with the following Fox formula. The weight ratio can be set.

_{1 / Tg = (W 1 /} Tg 1) + (W 2 / Tg 2) + ... + (W m / Tg m)
W ₁ + W ₂ + ... + W _m = 1
In the formula, Tg represents the glass transition temperature of the polymer portion, and Tg ₁ , Tg ₂ ,..., Tg _m represent the glass transition temperature of the homopolymer of each polymerization monomer. W ₁ , W ₂ ,..., W _m represent the weight ratio of each polymerization monomer.

  As the glass transition temperature of the homopolymer of each polymerization monomer in the Fox formula, for example, a value described in Polymer Handbook Fourth Edition (Wiley-Interscience, 1999) may be used. The glass transition temperature can be measured by DSC (differential scanning calorimetry) or tan δ peak of dynamic viscoelasticity. However, the (meth) acrylic polymer block (a) and the acrylic polymer block (b ) Are too close or the number of block monomer chains is too small, the measured values may deviate from the calculation formula according to the Fox equation.

≪ (Meth) acrylic polymer block (a) ≫
The monomer constituting the (meth) acrylic polymer block (a) is easy to obtain the desired physical property (meth) acrylic block copolymer (A), from the viewpoint of cost and availability. It consists of 50 to 100% by weight of methacrylic acid ester and 0 to 50% by weight, preferably 0 to 25% by weight, of other vinyl monomers copolymerizable therewith. When the proportion of the methacrylic acid ester is less than 50% by weight, the weather resistance, high glass transition point, compatibility with the resin, etc., which are the characteristics of the methacrylic acid ester, tend to be impaired. In addition, when the functional group (c) described later is included in the (meth) acrylic polymer block (a), it becomes a monomer having the functional group (c) or a precursor of the functional group (c). The monomer having a functional group is preferably a methacrylic acid ester or another vinyl monomer copolymerizable therewith.

  The molecular weight required for the (meth) acrylic polymer block (a) may be determined from the cohesive force required for the (meth) acrylic polymer block (a) and the time required for the polymerization. .

The cohesive force is said to depend on the interaction between molecules (in other words, polarity) and the degree of entanglement. As the molecular weight increases, the entanglement point increases and the cohesive force increases. That is, (meth) Ma molecular weight required for the acrylic polymer block (a) and M _a, a (meth) between polymer entanglement points constituting the acrylic polymer block (a) molecular weight as M _ca For example, when cohesion is required, preferably M _a > M _ca. To further illustrate, when more cohesive force is required, preferably M _a > 2 × M _ca , and conversely, when it is desired to achieve a certain level of cohesive force and creep properties, M _ca < M _a <2 × M _ca is preferred. For the molecular weight between the entanglement points, reference may be made to Wu et al. (Polym. Eng. And Sci., 1990, 30, 753). For example, assuming that the (meth) acrylic polymer block (a) is entirely composed of methyl methacrylate, the number average molecular weight of the (meth) acrylic polymer block (a) when cohesion is required For example, the range is preferably 9200 or more. However, since the polymerization time tends to be long when the number average molecular weight is large, the polymerization time may be set according to the required productivity, but is preferably 200000 or less, more preferably 100000 or less. However, when the functional group (c) described later is contained in the (meth) acrylic polymer block (a) and the cohesive force is imparted by the functional group (c), the molecular weight is set lower than this. can do.

  Examples of the methacrylic acid ester constituting the (meth) acrylic polymer block (a) include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, T-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, methacrylic acid Methacrylic acid aliphatic hydrocarbons (eg alkyl) esters such as myristyl, palmityl methacrylate, stearyl methacrylate; methacrylic acid alicyclic hydrocarbon esters such as cyclohexyl methacrylate and isobornyl methacrylate Methacrylic acid aralkyl esters such as benzyl methacrylate; methacrylic aromatic hydrocarbon esters such as phenyl methacrylate and toluyl methacrylate; methacrylic acid and ethereal oxygen such as 2-methoxyethyl methacrylate and 3-methoxybutyl methacrylate An ester with a functional group-containing alcohol having: trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methacrylate, 2-perfluoromethyl-2-perfluoroethyl methacrylate, 2-par methacrylate Fluorohexyl ethyl, 2-perfluoro decyl ethyl methacrylate acid and methacrylic acid fluorinated alkyl esters such as methacrylic acid 2-perfluoroalkyl-hexadecyl ethyl. 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) ) Dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, these may be used alone or in combination of two or more thereof. Among these, methyl methacrylate is preferable in terms of cost, availability, and cohesion.

  Examples of vinyl monomers copolymerizable with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include acrylic acid esters, aromatic alkenyl compounds, vinyl cyanide compounds, and conjugated diene compounds. , Halogen-containing unsaturated compounds, silicon-containing unsaturated compounds, unsaturated carboxylic acid compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, maleimide compounds, and the like.

  Examples of the acrylic acid ester copolymerizable with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and acrylic acid. n-butyl, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, acrylic acid Acrylic aliphatic hydrocarbon (eg alkyl) esters such as decyl, lauryl acrylate, myristyl acrylate, palmityl acrylate, stearyl acrylate; acrylate cycloaliphatic hydrocarbon esters such as cyclohexyl acrylate, isobornyl acrylate; Acrylic aromatic hydrocarbon esters such as phenyl acid and toluyl acrylate; Aralkyl esters of acrylic acid such as benzyl acrylate; Functionalities having acrylic acid and etheric oxygen such as 2-methoxyethyl acrylate and 3-methoxybutyl acrylate Esters with group-containing alcohols; trifluoromethyl methyl acrylate, 2-trifluoromethyl ethyl acrylate, 2-perfluoroethyl ethyl acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl acrylate, acrylic acid 2 -Perfluoroethyl, perfluoromethyl acrylate, diperfluoromethyl methyl acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl acrylate, 2-perfluorohexyl ethyl acrylate, 2-perf acrylate Fluoroalkyl acrylate such as orodecylethyl, 2-perfluorohexadecylethyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, acrylic acid Examples include 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, an ethylene oxide adduct of acrylic acid, and the like.

  Examples of the aromatic alkenyl compound copolymerizable with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene. be able to.

  Examples of the vinyl cyanide compound copolymerizable with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include acrylonitrile and methacrylonitrile.

  Examples of the conjugated diene compound that can be copolymerized with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include butadiene and isoprene.

  Examples of the halogen-containing unsaturated compound copolymerizable with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, vinylidene fluoride, and the like. Can be mentioned.

  Examples of the silicon-containing unsaturated compound copolymerizable with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include vinyltrimethoxysilane and vinyltriethoxysilane.

  Examples of the unsaturated carboxylic acid compound copolymerizable with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include methacrylic acid and acrylic acid.

  Examples of the unsaturated dicarboxylic acid compound copolymerizable with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include, for example, maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid, fumarate Examples thereof include monoalkyl esters and dialkyl esters of acids and fumaric acids.

  Examples of vinyl ester compounds copolymerizable with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate. Can be mentioned.

  Examples of maleimide compounds copolymerizable with the methacrylic acid ester constituting the (meth) acrylic acid polymer block (a) include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, Examples thereof include dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide and the like.

  These vinyl monomers constituting the (meth) acrylic acid polymer block (a) are used alone or in combination of two or more thereof. These vinyl monomers are required for the (meth) acrylic block copolymer (A) and, as will be described later, a (meth) acrylic polymer (B) having a reactive functional group at the terminal. A preferable one can be selected according to the compatibility with (A). In addition, methyl methacrylate polymer is almost quantitatively depolymerized by thermal decomposition, but in order to suppress it, acrylic acid esters such as methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic Acid 2-methoxyethyl or a mixture thereof, or styrene can be copolymerized.

  The glass transition temperature of the (meth) acrylic polymer block (a) is preferably 25 ° C. or higher, more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, more preferably 100 ° C. or higher, particularly preferably 105 ° C. or higher. Most preferably, it is 110 ° C. or higher. When the glass transition temperature of the (meth) acrylic polymer block (a) is lower than 25 ° C., the moldability tends to deteriorate. On the other hand, when the glass transition temperature is less than 100 ° C., the heat resistance as a thermoplastic elastomer is insufficient, that is, the rubber elasticity at a high temperature tends to decrease.

  The glass transition temperature (Tg) of the (meth) acrylic polymer block (a) can be set by setting the monomer weight ratio of each polymer portion according to the Fox formula.

≪Acrylic polymer block (b) ≫
The monomer constituting the acrylic polymer block (b) is 50 to 100% by weight of an acrylate ester and is coexistent with it from the viewpoint of easily obtaining a composition having desired physical properties, cost and availability. It consists of 0 to 50% by weight of a polymerizable vinyl monomer, preferably 0 to 25% by weight. If the proportion of the acrylate ester is less than 50% by weight, the physical properties of the composition, particularly impact resistance and flexibility, which are characteristic when the acrylate ester is used, tend to be impaired.

  The molecular weight required for the acrylic polymer block (b) may be determined from the elastic modulus and rubber elasticity required for the acrylic polymer block (b), the time required for the polymerization, and the like.

The elastic modulus is closely related to the ease of movement of the molecular chain (in other words, the glass transition temperature) and the molecular weight thereof, and the original elastic modulus is not exhibited unless the molecular weight exceeds a certain level. The same applies to rubber elasticity, but from the viewpoint of rubber elasticity, a higher molecular weight is desirable. That is, when the molecular weight required for the acrylic polymer block (b) is M _b , the range is exemplified. Preferably, M _b > 3000, more preferably M _b > 5000, more preferably M _b > 10000, Preferably M _b > 20000, most preferably M _b > 40000. However, since the polymerization time tends to be longer when the number average molecular weight is large, the polymerization time may be set according to the required productivity, but is preferably 500,000 or less, more preferably 300,000 or less.

  Examples of the acrylate ester constituting the acrylic polymer block (b) include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid t -Butyl, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, myristyl acrylate, acrylic Acrylic aliphatic hydrocarbon (eg alkyl) esters such as palmitic acid, stearyl acrylate, etc .; Acrylic alicyclic hydrocarbon esters such as cyclohexyl acrylate, isobornyl acrylate; phenyl acrylate, toluyl acrylate, etc. Aryl hydrocarbon aromatic ester; aralkyl ester of acrylic acid such as benzyl acrylate; ester of acrylic acid such as 2-methoxyethyl acrylate and 3-methoxybutyl acrylate and functional group-containing alcohol having etheric oxygen; acrylic Acid trifluoromethylmethyl, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoroethyl acrylate Fluoromethyl, diperfluoromethyl methyl acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl acrylate, 2-perfluorohexyl ethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perf acrylate Fluoroalkyl acrylates such as olohexadecylethyl, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, γ- (methacryloyl) Oxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, and the like. These may be used alone or in combination of two or more thereof.

  Among these, n-butyl acrylate is preferable in terms of impact resistance, flexibility, cost, and availability of the composition of the present invention. Moreover, n-ethyl acrylate is preferable when the composition requires polarity and oil resistance. Moreover, 2-ethylhexyl acrylate is preferable when the composition requires polarity and low temperature characteristics. Furthermore, a mixture of n-ethyl acrylate, n-butyl acrylate, and 2-methoxyethyl acrylate is preferred when it is desired to achieve both polarity, oil resistance and low-temperature characteristics.

  Examples of the vinyl monomer copolymerizable with the acrylic ester constituting the acrylic polymer block (b) include, for example, a methacrylic ester, an aromatic alkenyl compound, a vinyl cyanide compound, a conjugated diene compound, and a halogen-containing compound. Examples include unsaturated compounds, silicon-containing unsaturated compounds, unsaturated carboxylic acid compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, and maleimide compounds.

  Examples of the methacrylic acid ester copolymerizable with the acrylic acid ester constituting the acrylic polymer block (b) include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n-butyl methacrylate. , Isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, methacryl Methacrylic acid aliphatic hydrocarbons (eg alkyl) esters such as lauryl acid, myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, etc .; metas such as cyclohexyl methacrylate and isobornyl methacrylate Alicyclic alicyclic hydrocarbon ester; Aralkyl methacrylate such as benzyl methacrylate; Aromatic hydrocarbon methacrylate such as phenyl methacrylate and toluyl methacrylate; 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, etc. Ester of methacrylic acid and functional group-containing alcohol having etheric oxygen; trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl methacrylate 2-perfluorobutylethyl, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-perfluoromethyl-2-perfluoroethyl methacrylate Methyl fluorinated alkyl esters such as chill, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxy methacrylate Examples thereof include propyl, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, and an ethylene oxide adduct of methacrylic acid.

  Examples of the aromatic alkenyl compound copolymerizable with the acrylate ester constituting the acrylic polymer block (b) include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like. .

  Examples of the vinyl cyanide compound copolymerizable with the acrylate ester constituting the acrylic polymer block (b) include acrylonitrile and methacrylonitrile.

  Examples of the conjugated diene compound that can be copolymerized with the acrylate ester constituting the acrylic polymer block (b) include butadiene and isoprene.

  Examples of the halogen-containing unsaturated compound copolymerizable with the acrylic acid ester constituting the acrylic polymer block (b) include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Can do.

  Examples of the silicon-containing unsaturated compound copolymerizable with the acrylic ester constituting the acrylic polymer block (b) include vinyltrimethoxysilane and vinyltriethoxysilane.

  Examples of the unsaturated carboxylic acid compound copolymerizable with the acrylic ester constituting the acrylic polymer block (b) include methacrylic acid and acrylic acid.

  Examples of unsaturated dicarboxylic acid compounds that can be copolymerized with the acrylic ester constituting the acrylic polymer block (b) include maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, fumaric acid, and the like. Examples thereof include monoalkyl esters and dialkyl esters of acids.

  Examples of the vinyl ester compound copolymerizable with the acrylate ester constituting the acrylic polymer block (b) include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and the like. it can.

  Examples of maleimide compounds that can be copolymerized with the acrylic acid ester constituting the acrylic polymer block (b) include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, Stearyl maleimide, phenyl maleimide, cyclohexyl maleimide and the like can be mentioned.

  These vinyl monomers constituting the acrylic polymer block (b) are used alone or in combination of two or more thereof. These vinyl monomers are composed of glass transition temperature, elastic modulus, polarity required for the acrylic polymer block (b), physical properties required for the composition, and reactive functional groups at the ends as described later. A preferable one can be selected depending on the compatibility with the (meth) acrylic polymer (B) having a group.

  The glass transition temperature of the acrylic polymer block (b) is preferably 25 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −20 ° C. or lower. When the glass transition temperature is higher than 25 ° C, the flexibility and low temperature characteristics of the composition of the present invention tend to be lowered.

≪ (Meth) acrylic block copolymer (A) functional group (c) ≫
The (meth) acrylic block copolymer (A) has the block structure as described above, but may further have a functional group (c). The functional group (c) is not particularly limited, and examples thereof include a reactive silicon group, an alkenyl group, a polymerizable double bond group, a halogen group, a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, and an amino group. It is done. One type of these functional groups may be used, or two or more types may be used in combination. When two or more kinds of functional groups are used in combination, the reaction modes are different, so that functional groups that do not react with each other may be selected, or functional groups that react with each other may be selected. Furthermore, even if the reaction mode is the same, functional groups having different reactivity and reaction conditions can be selected, and can be used properly according to the purpose.

  These functional groups (c) have a strong cohesive force, and polymers having these functional groups have a high glass transition temperature (Tg) and improve the thermal decomposition resistance of the (meth) acrylic block copolymer (A). Has an effect. Furthermore, the functional group (c) introduced into the (meth) acrylic block copolymer (A) can be used as a crosslinking point of the curable composition of the present invention.

  Among the functional groups (c), a carboxyl group is particularly preferable. The carboxyl group has a particularly strong cohesive force, and the glass transition temperature of the polymer having a carboxyl group is, for example, as high as 228 ° C. for polymethacrylic acid and 106 ° C. for polyacrylic acid. ) The thermal decomposition resistance of the acrylic block copolymer (A) can be improved.

  The method for introducing the functional group (c) is not particularly limited, but is conventionally disclosed in JP-A-10-298248, JP-A-2001-234146, International Publication WO2003 / 068888, JP-A-2008-248233, and the like. A known method can be used. That is, when the monomer having a functional group does not poison the catalyst under polymerization conditions, it is preferably introduced by direct polymerization, and when the monomer having a functional group deactivates the catalyst during polymerization For this, a method of introducing the functional group (c) by functional group conversion is preferable. In the method of introducing the functional group (c) by functional group conversion, the functional group (c) is protected with an appropriate protecting group, or in the form of a functional group that is a precursor of the functional group (c) (meta ) It can introduce | transduce into an acryl-type block copolymer, and can produce | generate a functional group by a well-known chemical reaction after that.

  The content of the functional group (c) contained in the (meth) acrylic block copolymer (A) used in the present invention is not particularly limited, and the structure of the (meth) acrylic block copolymer (A) and It varies depending on the composition, the number of blocks constituting the (meth) acrylic block copolymer (A), and the site and manner in which the functional group is contained. Moreover, the functional group (c) may not be contained. However, in the case of expecting an effect as a cohesive force and a crosslinking point due to the functional group (c), a preferable range of the content of the functional group (c) is exemplified. When importance is attached to the physical property balance of the composition, Preferably, it is 0.1 or more on average per molecule of the (meth) acrylic block copolymer (A), more preferably 0.2 or more, and further preferably 0.5 or more. There is no upper limit of the content of the functional group (c), and the functional group (c) can be contained in all the monomers constituting the (meth) acrylic polymer block (a). When the functional group (c) is contained in the (meth) acrylic block copolymer (A), the content of the functional group (c) constitutes the (meth) acrylic polymer block (a). Among the monomers, the content of the monomer having the functional group (c) is preferably 5% by weight or more. This is because by introducing these monomers having a high Tg into the hard segment, rubber elasticity can be exhibited even at high temperatures. More preferably, the content of the monomer having the functional group (c) is 5 to 99.9% by weight. When the content of the monomer having the functional group (c) is less than 5% by weight, the cohesive strength and heat resistance of the (meth) acrylic polymer block are insufficient and the rubber elasticity is exhibited at high temperature. Tend to decrease. If it exceeds 99.9% by weight, it tends to be difficult in production.

  The functional group (c) may be contained in the (meth) acrylic polymer block (a) or at the boundary between the (meth) acrylic polymer block (a) and the acrylic polymer block (b). It may be contained, and may be contained at the molecular chain terminal of the (meth) acrylic block copolymer (A). The manner in which the functional group (c) is contained is not particularly limited, but it can be derived from a monomer, or can be bound to the molecular chain directly or via an appropriate organic group. When the functional group (c) is derived from a monomer, the number of repeating units composed of the monomer can be 1 or 2 or more per polymer block containing the monomer, and the number Is 2 or more, the mode in which the monomer is polymerized can be random copolymerization or block copolymerization.

  Taking an ab type diblock copolymer as an example, it may be any of (a / c) -b type, cab type, acb type, and the like. For example, the a-b-a type triblock copolymer is represented by (a / c) -ba type, (a / c) -b- (a / c) type, c-ab- Any of a-type, c-a-b-a-c type, etc. may be sufficient. Here, (a / c) represents that the (meth) acrylic polymer block (a) contains the functional group (c). When two or more types of functional groups (c) are used in combination, the contained sites and the contained modes may be freely set within the above ranges, and can be properly used according to the purpose.

≪Blend with (meth) acrylic polymer (B) and acrylic block copolymer (A) ≫
The present invention includes (a) a (meth) acrylic polymer block and (b) a (meth) acrylic block copolymer (A) containing an acrylic polymer block, and at least one terminal reactive functional group. The present invention relates to a curable composition comprising a (meth) acrylic polymer (B) having a group.

  Although the monomer which comprises a (meth) acrylic-type block copolymer (A) and the monomer which comprises a (meth) acrylic-type polymer (B) are not specifically limited, There may exist the same thing. And may be different. However, in consideration of the compatibility between the monomer constituting the (meth) acrylic block copolymer (A) and the (meth) acrylic polymer (B), it is preferable that the same one is included. . In this case, the same monomer as that constituting the (meth) acrylic polymer (B) is not particularly limited, but (meth) in the (meth) acrylic block copolymer (A). It may be contained in the acrylic polymer block (a) or may be contained in the acrylic polymer block (b). If the same monomer as that constituting the (meth) acrylic polymer (B) is contained in the (meth) acrylic polymer block (a), a high-strength curable composition is obtained. If it is included in the acrylic polymer block (b), a curable composition having excellent flexibility can be obtained.

  The amount of the same monomer structure as the (meth) acrylic polymer (B) contained in the (meth) acrylic block copolymer (A) is not particularly limited. The compatibility between the polymer (B) and the (meth) acrylic block copolymer (A) is increased, which is preferable. That is, the monomer identical to the monomer constituting the (meth) acrylic polymer (B) is not particularly limited, but the (meth) acrylic in the (meth) acrylic block copolymer (A). It is preferable that 50% by weight or more is contained in any block of the polymer block (a) or the acrylic polymer block (b), more preferably 60% by weight or more, still more preferably 70% by weight or more, 80% by weight or more is particularly preferable.

  In the curable composition of the present invention, the blend ratio of the (meth) acrylic polymer (B) and the (meth) acrylic block copolymer (B) is not particularly limited. The (meth) acrylic block copolymer (A) is used in an amount of 1 to 500 parts by weight based on 100 parts by weight of the combined body (B). A preferable blend ratio is 2 to 300 parts by weight, more preferably 3 to 200 parts by weight, still more preferably 4 to 100 parts by weight, and particularly preferably 5 to 50 parts by weight. When the addition amount of the (meth) acrylic block copolymer (B) is small, effects such as strength improvement by the (meth) acrylic block copolymer (B) may not be expressed. Moreover, when there are too many addition amounts of a (meth) acrylic-type block copolymer (B), the fluidity | liquidity of the curable composition of this invention and the softness | flexibility of hardened | cured material may be impaired.

<< Method for producing (meth) acrylic polymer (B) and acrylic block copolymer (A) >>
As a method for producing a (meth) acrylic polymer (B) having a reactive functional group at at least one terminal and a (meth) acrylic block copolymer (A) used in the present invention, It is not limited, A conventionally well-known radical polymerization and anion polymerization can be used. However, since any polymer needs to have a high molecular structure, controlled polymerization is preferred among them. Examples of the controlled polymerization include living anion polymerization, coordination anion polymerization, radical polymerization using a chain transfer agent, and living radical polymerization recently developed. Here, in the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but in general, pseudo-living polymerization in which the terminal is inactivated and the terminal is in an equilibrium state. Is also included. The definition here is also the latter.

  Although it does not specifically limit as living anion polymerization, For example, the conventionally well-known method disclosed in international publication WO2004 / 041886 etc. can be used. Although it does not specifically limit as coordination anion polymerization, For example, the conventionally well-known method disclosed by Unexamined-Japanese-Patent No. 10-298248 can be used.

  Although it does not specifically limit as living radical polymerization, For example, J.Am.Chem.Soc., 1995,117,5614, J.Am.Chem.Soc., 2006,128,14156, international publication WO96 / 30421 , International Publication WO97 / 18247, JP2000-072809A, JP2001-234146A, JP2003-252940A, and the like can be used. The terminal functional group of the (meth) acrylic polymer (B) used in the present invention is not particularly limited. For example, the conventional functional groups disclosed in JP-A-2000-044626, JP-A-2000-191728, etc. It can be introduced by a known method.

≪Composition comprising (meth) acrylic polymer (B) and acrylic block copolymer (A) ≫
The present invention relates to a curable composition comprising a (meth) acrylic block copolymer (A) and a (meth) acrylic polymer (B), and various additions may be added to the composition as necessary. An agent may be added. The additive is not particularly limited, and if necessary, a plasticizer, a filler, a flexibility imparting agent, an adhesion imparting agent, an impact resistance improving agent, a foaming agent, a lubricant, a curing catalyst, a crosslinking agent, an antioxidant, Examples include decomposition inhibitors, ultraviolet absorbers, dehydrating agents, storage stability improvers, metal deactivators, antistatic agents, antibacterial and antifungal agents, flame retardants, pigments, decolorizing agents, and solvents.

  Applications of the curable composition of the present invention include, but are not limited to, electrical / electronic components (heavy electrical components, weak electrical components, electrical / electronic equipment circuits and circuit board sealing materials (refrigerators, freezers, washing machines, gas meters, Microwave oven, steam iron or earth leakage breaker sealant), potting material (transformer high voltage circuit, printed circuit board, high voltage transformer with variable resistance, electrical insulation component, semiconductive component, conductive component, solar cell or TV fly Potting of back transformer), coating material (thick film resistor for high voltage or hybrid IC circuit element; HIC; electrical insulation component; semiconductive component; conductive component; module; printed circuit; ceramic substrate; diode, transistor or bonding wire Buffer materials; semi-conductor elements; or optical communications optics Fiber coating), resist material (semiconductor resist, liquid solder resist, electrodeposition resist, dry film resist, liquid crystal photoresist, permanent resist, etc.) or adhesive (CRT wedge, neck, electrical insulation component, semiconductive component or Adhesive of conductive parts); Repair material for wire coating; Insulation sealing material for wire joint parts; Roll for office automation equipment; Vibration absorber; Or encapsulation of gel or capacitor), Automobile parts (Automobile engine gaskets, electrical parts or oil filters) Sealing materials for automobiles; Bottling materials for igniter HICs or hybrid ICs for automobiles; Coating materials for automobile bodies, automobile window glass or engine control boards; or gaskets for oil pans, timing belt covers Adhesives for skets, moldings, headlamp lenses, sunroof seals or mirrors; fuel injection devices, fuel heating devices, air dampers, pressure detection devices, oil coolers for resin tanks for heat exchangers, variable compression ratio engines, cylinder devices, compression natural Gas regulators, pressure vessels, fuel supply systems for in-cylinder direct injection internal combustion engines or O-rings for high-pressure pumps, ships (wiring connection branch boxes, electrical system parts or sealing materials for electric wires; or bonding for electric wires or glass Agents), aircraft or railway vehicles, civil engineering / architecture (joint joints for glass screens in commercial buildings, joints around glass with sashes, interior joints in toilets, washrooms or showcases, joints around bathtubs, prefabricated houses For outer wall expansion joints and sizing board joints Sealant for materials; Sealant for double-glazed glass; Sealant for civil engineering used for road repair; Paint / adhesive for metal, glass, stone, slate, concrete or roof tile; or adhesive sheet, waterproof sheet or vibration-proof sheet) , Medical (sealing material for medical rubber stopper, syringe gasket or rubber stopper for decompression blood vessel) or recreation (swimming cap, diving mask or earplug swimming member; or gel cushion for sports shoes or baseball glove) It can be used for various purposes.

  Specific examples of the present invention are shown below, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “part” and “%” represent “part by weight” and “% by weight”, respectively. “Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804 + K-802.5; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.

The functional groups that are introduced into the polymer per molecule, the concentration analysis by ¹ H-NMR, and was calculated based on the number average molecular weight found by GPC. NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.

(Synthesis Example 1)
Synthesis of acrylic polymer [B-1] having a polymerizable double bond at the terminal 100 parts of n-butyl acrylate was weighed and purged with nitrogen. 40 parts of this n-butyl acrylate, 0.42 part of copper (I) bromide, and 8.8 parts of acetonitrile were charged and stirred at 80 ° C. in a nitrogen stream. To this, 1.8 parts of diethyl 2,5-dibromoadipate was added, and the mixture was further stirred at 80 ° C. To this, 0.034 parts of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate the reaction. On the way, the remaining 60 parts of n-butyl acrylate were added intermittently. Furthermore, heating and stirring were continued so that the temperature of the reaction solution became 80 ° C to 90 ° C while adding triamine as appropriate. After the reaction rate of butyl acrylate reached 95%, the inside of the reaction vessel was depressurized to remove volatile components. The total amount of triamine added so far was 0.15 part.

  This was diluted with butyl acetate, synthetic hydrotalcite, aluminum silicate, and filter aid were added, and the mixture was heated and stirred in an oxygen / nitrogen mixed gas atmosphere. After removing solids, the solution was concentrated. This was diluted with N, N-dimethylacetamide and stirred with heating at 70 ° C. for 3 hours in the presence of potassium acrylate. After concentration, the solid content was removed by diluting with butyl acetate, and then the volatile content was removed to obtain an acrylic polymer [B-1] having a polymerizable double bond at the terminal.

  The polymer [B-1] has an acryloyl group at both molecular ends. The number average molecular weight of the polymer [1] was 22400, the molecular weight distribution was 1.2, and the average number of acryloyl groups introduced per polymer molecule was 1.9.

(Synthesis Example 2)
Synthesis of PMMA-b-PBA-b-PMMA type block copolymer (composition ratio MMA / BA = 3/7) Nitrogen-substituted 2m ³ reactor with cuprous bromide 2.3kg, acetonitrile 28.5kg and acrylic 325 kg of acid-n-butyl and 2.3 kg of diethyl 2,5-dibromoadipate were charged, and the mixture was stirred for 30 minutes while raising the temperature to 70 ° C. 275 g of pentamethyldiethylenetriamine was added to start polymerization of acrylic acid-n-butyl serving as the first block. When the conversion rate reached 99%, 323 kg of toluene, 1.6 kg of cuprous chloride and 140 kg of methyl methacrylate were charged, and 275 g of pentamethyldiethylenetriamine was added to start polymerization of methyl methacrylate as the second block. Pentamethyldiethylenetriamine was appropriately added to adjust the reaction rate. When the conversion rate reached 90%, 980 kg of toluene was added to dilute the reaction solution, and the reactor was cooled to stop the polymerization, whereby PMMA-b-PBA-b-PMMA type (composition ratio MMA / BA = (3/7) (meth) acrylic polymer [A-2] was obtained.

  When the obtained (meth) acrylic polymer [A-2] was subjected to GPC analysis, the number average molecular weight Mn was 99,800, and the molecular weight distribution Mw / Mn was 1.39. The obtained (meth) acrylic polymer [A-2] was made into a cylindrical pellet having a diameter of about 3 mm by the following operation. That is, toluene and p-toluenesulfonic acid were added to the polymerization solution, and the mixture was stirred at room temperature for 3 hours in a nitrogen atmosphere. Solids were removed from this solution, aluminum silicate was added, and the mixture was stirred at room temperature for 3 hours under a nitrogen atmosphere. After removing solids from this solution, the solvent and unreacted monomer were evaporated using a horizontal evaporator. The obtained resin was pelletized with a pelletizer.

(Synthesis Example 3)
Synthesis of PMMA-b-PBA-b-PMMA type block copolymer (composition ratio MMA / BA = 2/8) 562 g of cuprous bromide, 8.3 kg of acetonitrile and acrylic acid-n in a 500 L reactor substituted with nitrogen -94.4 kg of butyl diethyl 564g of 2,5-dibromoadipate was charged and stirred for 30 minutes while the temperature was raised to 70 ° C. 68 g of pentamethyldiethylenetriamine was added, and polymerization of acrylic acid-n-butyl serving as the first block was started. When the conversion rate reached 98%, 54.1 kg of toluene, 388 g of cuprous chloride and 23.4 kg of methyl methacrylate were charged, and 68 g of pentamethyldiethylenetriamine was added to start polymerization of methyl methacrylate as the second block. did. Pentamethyldiethylenetriamine was appropriately added to adjust the reaction rate. When the conversion rate reached 90%, 281 kg of toluene was added to dilute the reaction solution, and the reactor was cooled to stop the polymerization, whereby PMMA-b-PBA-b-PMMA type (composition ratio MMA / BA = 2/8) (meth) acrylic polymer [A-2] was obtained.

  When the obtained (meth) acrylic polymer [A-2] was subjected to GPC analysis, the number average molecular weight Mn was 110,000, and the molecular weight distribution Mw / Mn was 1.32. The obtained (meth) acrylic polymer [A-2] was made into a cylindrical pellet having a diameter of about 3 mm by the following operation. That is, p-toluenesulfonic acid was added to the polymerization solution, and the mixture was stirred at room temperature for 3 hours in a nitrogen atmosphere. Solids were removed from this solution, aluminum silicate was added, and the mixture was stirred at room temperature for 3 hours under a nitrogen atmosphere. After removing solids from this solution, the solvent and unreacted monomer were evaporated using a horizontal evaporator. The obtained resin was pelletized with a pelletizer.

Example 1
100 parts of the acrylic polymer [B-1] obtained in Synthesis Example 1 as the (meth) acrylic polymer (B) having a reactive functional group at the terminal, (meth) acrylic block copolymer (A ) 10 parts of the (meth) acrylic polymer [A-1] obtained in Synthesis Example 2 as a photo radical initiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR1173) Ciba Specialty Chemicals) 0.1 parts, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE819; Ciba Specialty Chemicals) 0.05 parts, and dissolved sufficiently. After mixing, defoaming was performed at 60 ° C. for 1 hour. At this time, the composition was uniformly compatible. Further, it was poured into a mold and passed through a UV irradiation apparatus (LH-6; manufactured by Fusion Japan Co., Ltd.). Lamp energy = 184 W / cm, irradiation distance 54 cm, and once cured at a speed of 1 m / min. A sheet was obtained (integrated light amount = 3030 mJ / cm ² ). The sheet was light yellow and transparent, and no phase separation was observed. Using the obtained cured product, DuroA hardness, tensile properties, and tear properties were measured. Table 1 shows the cured product composition and results.

(Example 2)
The same operation as in Example 1 was carried out except that the (meth) acrylic polymer [A-2] obtained in Synthesis Example 3 was used as the (meth) acrylic block copolymer (A). It was created. At this time, the composition was uniformly compatible. Further, the same operation as in Example 1 was performed and UV irradiation was performed to obtain a sheet having a thickness of 2 mm. The sheet was light yellow and transparent, and no phase separation was observed. Using the obtained cured product, DuroA hardness, tensile properties, and tear properties were measured. Table 1 shows the cured product composition and the results.

(Comparative Example 1)
A sheet having a thickness of 2 mm was obtained in the same manner as in Example 1 except that the (meth) acrylic block copolymer (A) was not added. Using the obtained cured product, DuroA hardness, tensile properties, and tear properties were measured. Table 1 shows the cured product composition and the results.
<Measurement method>
Duro A hardness: According to JIS K6253, three sheets of 20 × 20 mm width were stacked and the hardness was measured. Rubber hardness was measured.
Tensile properties: In accordance with JIS K6251, dumbbell-shaped No. 3 test pieces were cut out and evaluated for tensile properties at a tensile speed of 200 mm / second.
Tear characteristics: In accordance with JIS K6252, angle-shaped test pieces without incisions were cut out, and the tear characteristics were evaluated at a tensile speed of 100 mm / sec.

  The cured product obtained from the curable composition added with the (meth) acrylic block copolymer (A) prepared in Example 1 and Example 2 was the (meth) acrylic prepared in Comparative Example 1. Compared with the hardened | cured material which did not add a block copolymer (A), tensile strength and tear strength improved, maintaining a softness | flexibility.

Claims (12)

2 components below;
(A): (a) (meth) acrylic polymer block and (b) (meth) acrylic block copolymer containing acrylic polymer block,
(B): A curable composition comprising a (meth) acrylic polymer having a reactive functional group at at least one terminal. The terminal reactive functional group of the (meth) acrylic polymer (B) is selected from the group consisting of a reactive silicon group, an alkenyl group, a polymerizable double bond group, a hydroxyl group, a carboxyl group, an epoxy group, and an amino group. The curable composition of claim 1, which is at least one group. The number average molecular weight (Mn) of a (meth) acrylic-type polymer (B) is 1000-200000, The curable composition as described in any one of Claims 1-2. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the (meth) acrylic polymer (B) is 1.8 or less. 4. The curable composition according to any one of 3. The curable composition according to any one of claims 1 to 4, wherein the main chain of the (meth) acrylic polymer (B) is composed of an acrylate ester. The (meth) acrylic block copolymer (A) is a (a)-(b)-(a) triblock copolymer or (a)-(b) diblock copolymer. The curable composition according to any one of 5. The number average molecular weight (Mn) of the (meth) acrylic block copolymer (A) is 10,000 to 500,000. The curable composition according to any one of claims 1 to 6. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the (meth) acrylic block copolymer (A) is 1.8 or less. The curable composition as described in any one of 1-7. A block copolymer in which the (meth) acrylic block copolymer (A) comprises (a) (meth) acrylic polymer block 5 to 90% by weight and (b) acrylic polymer block 95 to 10% by weight. The curable composition according to any one of claims 1 to 8. In the (meth) acrylic block copolymer (A), 50% by weight or more of the monomer units constituting either the (a) (meth) acrylic polymer block or the (b) acrylic polymer block is The curable composition as described in any one of Claims 1-9 in the case where it is the same as the monomer unit which comprises a (meth) acrylic-type polymer (B). The (meth) acrylic block copolymer (A) further comprises a reactive silicon group, alkenyl group, polymerizable double bond group, halogen group, hydroxyl group, carboxyl group, acid anhydride group, epoxy group, amino group. The curable composition according to any one of claims 1 to 10, which is a block polymer having at least one group selected from the group consisting of: The blend ratio of the (meth) acrylic polymer (B) and the (meth) acrylic block copolymer (A) is (meth) acrylic with respect to 100 parts by weight of the (meth) acrylic polymer (B). The curable composition as described in any one of Claims 1-11 in case a system block copolymer (A) is 1-500 weight part.