WO2019131374A1 - ゴム含有グラフト重合体、ゴム含有グラフト重合体含有樹脂組成物およびその成形体 - Google Patents
ゴム含有グラフト重合体、ゴム含有グラフト重合体含有樹脂組成物およびその成形体 Download PDFInfo
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- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular 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
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
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Definitions
- the present invention relates to a rubber-containing graft polymer, a rubber-containing graft polymer-containing resin composition, and a molded article thereof.
- Priority is claimed on Japanese Patent Application No. 2017-247766, filed Dec. 25, 2017, the content of which is incorporated herein by reference.
- the rubber-containing graft polymer is obtained by graft polymerizing a vinyl monomer to a rubbery polymer.
- the rubber-containing graft polymer is produced by emulsion polymerization and can be dispersed in a wide variety of resins while maintaining a predetermined rubber particle diameter and rubber structure, and therefore, it is suitably used as a resin for which impact strength is required.
- methyl methacrylate is suitably used as the vinyl monomer.
- thermoplastic resins such as polycarbonates, styrenic resins and polyvinyl chloride resins.
- the rubber dispersibility in the resin is not sufficient, and the rubber is a resin under ordinary melt-kneading conditions (extrusion conditions) It tends to aggregate inside.
- the rubber when used in an alloy in which two or more types of resins are mixed, due to the difference in compatibility with methyl methacrylate, the rubber tends to be unevenly distributed in either resin, and sufficient impact strength can not be obtained.
- thermoplastic resins are used in various applications such as home appliances, office automation equipment, automobile parts, etc.
- the size of the molded body has become larger and the shape has become more complex, and multipoint gates are being used. Injection molding by the method has come to be performed.
- the multipoint gate method when molten resin joins and fuses in a mold, a fragile portion called weld is formed. Since weld causes a reduction in strength, improvement in the strength (weld strength) of the weld portion is required.
- Patent Document 1 discloses an example in which a rubber-containing graft polymer obtained by graft polymerization of a vinyl monomer containing methyl methacrylate as a main component to a butadiene-based rubber is blended in an alloy of a polycarbonate resin and a styrene acrylonitrile resin. There is. However, when the graft chain is methyl methacrylate, the low temperature impact strength and the weld strength are not satisfactory because the dispersion of the rubber in the resin is insufficient.
- Patent Document 2 discloses a rubber-containing graft polymer obtained by graft polymerizing glycidyl methacrylate and methyl methacrylate on silicone rubber. Since glycidyl methacrylate has an epoxy group, it chemically bonds with polycarbonate resin and polyester resin. Therefore, it is considered that the rubber can be uniformly dispersed in the resin by copolymerizing glycidyl methacrylate in the graft chain. However, since the epoxy group causes crosslinking in the thermoplastic resin or the rubber-containing graft polymer, the fluidity may be reduced by the amount of the epoxy group. In addition, even if the amount of epoxy groups is adjusted, sufficient mechanical strength (impact strength, weld strength, etc.) can not be obtained.
- Patent Document 3 discloses a rubber-containing graft polymer obtained by graft polymerization of 2-hydroxyethyl methacrylate and methyl methacrylate on acrylic rubber.
- a rubber-containing graft polymer obtained by graft polymerization of 2-hydroxyethyl methacrylate and methyl methacrylate on acrylic rubber.
- a thermoplastic resin having an ester bond such as a polycarbonate resin or a polyester resin
- the hydroxy group of the graft chain forms a covalent bond accompanied by a chemical reaction with the ester bond portion, and the rubber is contained in the resin. May be dispersed uniformly, but the weld strength has not been improved.
- incorporation of a fatty acid ester, especially a chain ester obtained by ring-opening a lactone ring such as a caprolactone ring, into a graft chain allows the rubber to be uniformly dispersed in a thermoplastic resin containing an alloy.
- the strength development required as a graft polymer can be improved.
- the present invention has the following aspects.
- a rubber-containing graft polymer having a graft chain which is When the rubber-containing graft polymer is mixed with an organic solvent and separated into an organic solvent insoluble portion and an organic solvent soluble portion, a rubber-containing graft weight containing a caprolactone unit in the graft chain contained in the organic solvent insoluble portion United.
- the composition contains 0.1 to 40 parts by mass of a caprolactone unit with respect to 100 parts by mass of a component having a glass transition temperature (Tg) of 60 ° C. or higher, which is contained in the graft chain of the organic solvent insolubles.
- Tg glass transition temperature
- the composition contains 0.5 to 30 parts by mass of a caprolactone unit with respect to 100 parts by mass of a component having a glass transition temperature (Tg) of 60 ° C. or higher, which is contained in the graft chain of the organic solvent insolubles.
- the composition contains 1.5 to 20 parts by mass of a caprolactone unit with respect to 100 parts by mass of a component having a glass transition temperature (Tg) of 60 ° C. or higher, which is contained in the graft chain of the organic solvent insolubles.
- Tg glass transition temperature
- the organic solvent insoluble matter is subjected to freeze grinding, and the freeze-ground organic solvent insoluble matter is mixed with the organic solvent, and separated into the organic solvent insoluble matter after freeze grinding and the organic solvent extract after freeze grinding
- the composition contains 0.1 to 40 parts by mass of a caprolactone unit with respect to 100 parts by mass of a component having a glass transition temperature (Tg) of 60 ° C. or higher, which is contained in the organic solvent extract after freeze grinding.
- Tg glass transition temperature
- the composition contains 0.5 to 30 parts by mass of a caprolactone unit with respect to 100 parts by mass of a component having a glass transition temperature (Tg) of 60 ° C. or higher, which is contained in the organic solvent extract after freeze grinding.
- the composition contains 1.5 to 20 parts by mass of a caprolactone unit with respect to 100 parts by mass of a component having a glass transition temperature (Tg) of 60 ° C. or higher, which is contained in the organic solvent extract after freeze grinding.
- Tg glass transition temperature
- the organic solvent insolubles are subjected to an ozone addition reaction, and the ozone added organic solvent insolubles are mixed with the organic solvent, and the organic solvent insolubles after the ozone addition reaction and the organic solvent extract after the ozone addition reaction
- the composition contains 0.1 to 40 parts by mass of a caprolactone unit with respect to 100 parts by mass of a component having a glass transition temperature (Tg) of 60 ° C. or higher contained in the organic solvent extract after the ozone addition reaction
- Tg glass transition temperature
- the composition contains 0.5 to 30 parts by mass of a caprolactone unit with respect to 100 parts by mass of a component having a glass transition temperature (Tg) of 60 ° C. or higher contained in the organic solvent extract after the ozone addition reaction 10]
- the composition contains 1.5 to 20 parts by mass of a caprolactone unit with respect to 100 parts by mass of a component having a glass transition temperature (Tg) of 60 ° C. or higher contained in the organic solvent extract after the ozone addition reaction 11]
- a rubber-containing graft polymer-containing resin composition comprising the rubber-containing graft polymer according to any one of [1] to [17] and a thermoplastic resin (B).
- the thermoplastic resin (B) is an alloy of an aromatic polycarbonate resin and a polyester resin.
- thermoplastic resin (B) is an alloy of an aromatic polycarbonate resin and a styrene resin.
- the molded article according to [22] which is an injection molded article.
- the rubber-containing graft polymer of the present invention can be uniformly dispersed in an alloy-containing thermoplastic resin at a rubber particle diameter of 50 to 400 nm, which was conventionally difficult. As a result, the mechanical strength such as weld strength and impact strength required as a rubber-containing graft polymer is excellent. Since the rubber-containing graft polymer-containing resin composition of the present invention contains the rubber-containing graft polymer of the present invention, the rubber-containing graft polymer can be uniformly dispersed in the resin composition, and the rubber-containing graft polymer of the present invention The molded article of the present invention formed by molding the graft polymer-containing resin composition is excellent in mechanical strength.
- the rubber-containing graft polymer of the present invention (hereinafter also referred to as "rubber-containing graft polymer (A)") is obtained by graft polymerization of a vinyl monomer to a rubbery polymer (rubber latex) ( Graft latex).
- the graft monomer (b) is graft-polymerized to a rubbery polymer obtained in an aqueous medium in the presence of an emulsifier, and may be produced by emulsion polymerization.
- the “grafted chain” is a vinyl polymer or vinyl copolymer formed by graft polymerization of a grafting monomer (b) which is chemically bonded to the rubber crosslinking component of the rubbery polymer described later.
- a glass transition temperature can use the thing of 0 degrees C or less.
- the impact strength represented by the value of the Charpy impact test of the molded article obtained from the resin composition of the present invention is improved.
- the rubbery polymer include the following. 1 type of vinyl monomer containing acrylate in the presence of rubbery polymer obtained from butadiene rubber, styrene-butadiene copolymer rubber, silicone rubber, silicone-acrylic composite rubber (monomer based on dimethylsiloxane) Or obtained by polymerizing two or more species), acrylonitrile-butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene-propylene rubber, ethylene-propylene-diene terpolymer Block copolymers such as rubber, styrene butadiene block copolymer rubber, styrene isoprene block copolymer rubber, and hydrogenated products thereof;
- butadiene rubbers having a glass transition temperature of -20 ° C or less butadiene rubbers having a glass transition temperature of -20 ° C or less, styrene-butadiene copolymer rubbers, silicone-acrylic composite rubbers Is preferred.
- the content of the rubbery polymer in the rubber-containing graft polymer (A) (100% by mass) is preferably in the range of 50 to 95% by mass, from the viewpoint of the impact strength of the molded article, 70 to 94%. % Is more preferable, 75 to 93% by mass is more preferable, 77 to 92% by mass is particularly preferable, and 80 to 91% by mass is most preferable.
- a component derived from graft polymerization (a component formed by graft polymerization of a grafting monomer (b) onto a rubbery polymer) constituting the rubber-containing graft polymer (A) is also referred to as a "graft component”. say.
- the rubber-containing graft polymer (A) of the present invention preferably contains, in the graft component, a unit derived from a vinyl monomer having a ring-opened lactone moiety.
- the vinyl monomer having the ring-opened lactone moiety is preferably a vinyl monomer (f-1) represented by the following general formula (1).
- CH 2 CR 1 COO (CH 2) q O [CO (CH 2) m O] n H ⁇ (1) (Wherein, R 1 represents hydrogen or a methyl group, q is 2 to 5, m is 3 to 10, n is an integer of 1 to 10)
- the graft component of the rubber-containing graft polymer (A) is preferably made of a copolymer of the vinyl monomer (f-1) represented by the general formula (1) and other vinyl monomers.
- a copolymer has a ring-opened lactone moiety at the end of the side chain, so a highly reactive primary hydroxyl group is located at the end of the side chain. It is possible to change the reactivity with the thermoplastic resin by changing the copolymerization ratio of the monomer (f-1) represented by the above general formula (1), and to adapt it to various applications Can.
- the copolymer of the vinyl monomer (f-1) represented by the above general formula (1) and other vinyl monomers has a repeating structure of a ring-opened lactone in the side chain, the hydroxyl group at the side chain terminal is Is present at a position distant from the main chain and is easy to react with the thermoplastic resin.
- hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate having a hydroxyl group at the side chain end
- the hydroxyl group at the end of the graft chain is located in the vicinity of the main chain skeleton, so the reactivity of the hydroxyl group is poor.
- 2-hydroxyethyl methacrylate is very soluble in water, so it is difficult to carry out emulsion polymerization.
- a caprolactone modified vinyl monomer is preferable in view of reactivity with a thermoplastic resin, and in particular, a vinyl monomer modified with caprolactone represented by the following general formula (2) (F-2) is preferably used.
- the vinyl monomer (f-2) represented by the general formula (2) is obtained by the addition reaction of a hydroxyl group-containing polymerizable unsaturated monomer and ⁇ -caprolactone. As q, an integer of 2 to 3 is preferable, and 2 is more preferable.
- caprolactone unit (CL) a moiety derived from ⁇ -caprolactone (—CO (CH 2 ) 5 O—) is referred to as “caprolactone unit (CL)”.
- the glass transition temperature is preferably It is preferable to select a vinyl monomer having a temperature of 60.degree. C. or more, more preferably 70.degree. C. or more, and still more preferably 80 to 120.degree. It is preferable from the point of).
- vinyl monomers include methyl methacrylate, styrene or acrylonitrile, which may be mixed.
- the other vinyl monomer is particularly preferably methyl methacrylate.
- the vinyl monomer mixture further contains a vinyl monomer within 5% by mass with respect to the total mass of the grafting monomer (b) to be graft-polymerized to the rubbery polymer.
- a vinyl monomer for example, aromatic vinyl compounds such as styrene or ⁇ -methylstyrene; acrylic esters such as methyl acrylate and butyl acrylate; methacrylic esters such as ethyl methacrylate And the like, which may be copolymerized with methyl methacrylate.
- a copolymer of methyl methacrylate and butyl acrylate is suitably used.
- the impact resistance and weld of the thermoplastic resin composition can be obtained by including in the "graft chain" a unit derived from the vinyl monomer (f-1), particularly a unit derived from the vinyl monomer (f-2).
- the strength can be improved.
- a graft chain containing a unit derived from a vinyl monomer (f-1), particularly a unit derived from a vinyl monomer (f-2) is an ester bond or a carbonate bond (—O—C (O Excellent compatibility with many thermoplastic resins such as polyester and polycarbonate due to their ability to form covalent bonds with various functional groups such as) -O-) and ester bonds of carbon-carbon bond and ring-opened lactone moiety. It is because it shows sex.
- the rubber-containing graft polymer of the present invention is derived from the vinyl monomer (f-1) in the "graft chain".
- a copolymer having a unit, particularly a unit derived from a vinyl monomer (f-2), at the side chain end of its graft chain the most water-resistant polycaprolactone structure among polyesters is obtained. As it exists, it exerts excellent hydrolysis resistance.
- the content of the vinyl monomer (f-1) and the vinyl monomer (f-2) is 0. 0.
- the content is preferably 5 to 51% by mass, more preferably 1.0 to 40% by mass, and still more preferably 2.5 to 30% by mass.
- the rubbery polymer includes a rubber crosslinking component which is a component which is crosslinked and insoluble in an organic solvent, and a rubber non-crosslinking component which is a component which is polymerized without being crosslinked. It is preferable that the content of the rubber crosslinking component in the rubbery polymer is high.
- the graft chain in the rubber-containing graft polymer of the present invention is a polymer having a unit derived from the grafting monomer (b) which is chemically bonded to the rubber crosslinking component in the rubbery polymer.
- the grafting monomer (b) to be subjected to graft polymerization is polymerized by "vinyl monomer mgp" which is actually chemically bonded to the rubbery polymer, and without being chemically bonded to the rubbery polymer, It can be classified into “vinyl monomer mfp" which produces a free polymer and "vinyl monomer mfm” which does not undergo polymerization reaction.
- graft chain of the present invention (Grafted chain in “Rg” described later).
- the content ratio of the vinyl monomer which is chemically bonded to the component "rubber crosslinking component” which is crosslinked and insoluble in the organic solvent is high.
- the rubber monomer graft polymer (A) in the vinyl monomer mgp chemically bonded to the rubbery polymer, when the amount of the vinyl monomer chemically bonded to the “rubber cross-linking component” is large, the thermoplastic resin (described later) The rubber is easily dispersed in B), and the interfacial strength between the thermoplastic resin (B) and the rubber is improved.
- the vinyl monomer mfm which does not undergo polymerization reaction is almost completely removed in the subsequent recovery step (the coagulation or spray recovery step described later and the step of drying the obtained powder).
- the rubber-containing graft polymer (A) of the present invention is composed of the following five components.
- Rg graft chain derived from the rubber crosslinking component and the grafting monomer (b) chemically bonded thereto
- R0 not grafted with the rubber crosslinking component
- Ng chemically bonded to the rubber non-crosslinking component
- "Free polymer Pf" Grafting monomer not grafted with rubbery polymer (b) Polymer or copolymer derived from
- the organic solvent insoluble matter of the rubber-containing graft polymer (A) is a component (Rg + R0) derived from the rubber crosslinking component.
- the graft chain derived from the chemically bonding grafting monomer (b) in Rg contains a component derived from the vinyl monomer (f-1) and a component derived from the vinyl monomer (f-1) Is preferably a component derived from the vinyl monomer (f-2).
- the rubber-containing graft polymer (A) can be separated into an organic solvent insoluble matter and an organic solvent soluble matter by mixing with the organic solvent.
- the organic solvent which can be used when separating into the organic solvent insoluble portion and the organic solvent soluble portion is one which does not chemically deteriorate the rubber-containing graft polymer (A), and the rubber-containing graft polymer (A)
- acetone and tetrahydrofuran can be mentioned. From the viewpoint of workability, acetone is preferable in that it is highly volatile and easy to distill off the solvent.
- tetrahydrofuran is preferred when the rubber-containing graft polymer (A) contains a structural unit derived from styrene.
- the organic solvent insoluble matter of the rubber-containing graft polymer (A) is obtained by sufficiently mixing the precisely weighed rubber-containing graft polymer sample and the organic solvent, leaving the mixture to stand, and centrifuging to separate the organic solvent soluble matter and the organic matter.
- the operation of separating the solvent insoluble matter is performed a plurality of times, and determination can be made by removing the organic solvent from the combined organic solvent insoluble matter.
- centrifuge at rotational speed: 14,000 rpm for 60 minutes if acetone is turbid, centrifuge at rotational speed: 14,000 rpm for 300 minutes, and acetone is soluble in non-turbid state Separate the insolubles from the min.
- 30 mL of acetone is again added to the obtained insoluble matter and dispersed, and centrifuged in a centrifuge to separate into soluble matter and insoluble matter Repeat the operation three times.
- the insoluble matter is centrifuged and then set in an inert oven (DN610I, manufactured by Yamato Scientific Co., Ltd.) under a nitrogen atmosphere and heated at 40 ° C.
- Acetone insoluble matter (mass%) ([W1] / [W0]) ⁇ 100
- the “rubber non-crosslinking component” is It can be judged that the amount is small enough, and the graft chain can be regarded as the same value as "free polymer Pf" (not grafted with rubbery polymer). In this case, the rubber-containing graft polymer (A) can be considered to be composed of the Rg and the "free polymer Pf".
- a unit derived from a ring-opened lactone specifically, a caprolactone unit ( CL)
- CL caprolactone unit
- the caprolactone unit (CL) is included in (hereinafter referred to as “freeze-ground organic solvent extract (fw)”).
- freeze-grinding the organic solvent insoluble portion of the rubber-containing graft polymer (A) it is possible to decompose the rubber-containing graft polymer (A) and preferentially take out the crosslinked graft chains.
- freeze grinding By freeze grinding, the cross-linked graft chains and part of the cross-linked rubber are extracted with an organic solvent.
- the fact that the caprolactone unit (CL) is included in the organic solvent extract (fw) after freeze-pulverization means that the caprolactone unit (CL) is included in the graft chain of the rubber-containing graft polymer (A). means.
- a caprolactone unit (CL) By including a caprolactone unit (CL) in the graft chain, it is possible to reduce the dependence of mechanical strength on molding process represented by impact strength.
- the proportion of caprolactone units (CL) is 0.1 to 40 parts by mass with respect to 100 parts by mass of the components contained in the organic solvent extract (fw) after freeze-pulverization and having a glass transition temperature (Tg) of 60 ° C. or higher And preferably 0.5 to 30 parts by mass, and particularly preferably 1.5 to 20 parts by mass. If the ratio of the caprolactone unit (CL) with respect to 100 mass parts of components whose glass transition temperature (Tg) is 60 ° C. or higher, contained in the organic solvent extract (fw) after freeze-pulverization, is a functional group Reacts with the matrix resin and the rubber is uniformly dispersed in the resin, so it is easy to develop excellent mechanical properties.
- the ratio of the caprolactone unit (CL) to 100 parts by mass of the component having a glass transition temperature (Tg) of 60 ° C. or higher, contained in the organic solvent extract (fw) after freeze-pulverization is a graft component It is easy to suppress that the Tg of the above becomes too low and the subsequent coagulation step becomes difficult.
- the freeze-ground organic solvent extract (fw) is obtained by freeze-pulverizing the finely divided organic solvent-insoluble portion of the rubber-containing graft polymer and then thoroughly mixing the freeze-ground organic solvent insoluble portion with the organic solvent After standing, the operation of separating the soluble matter and the insoluble matter by centrifugation is performed several times, and quantification can be performed by removing the organic solvent from the combined soluble matter.
- Freeze-grinding (SPEX CertiPrep Ltd., product name: SPEX 6750 FREEZER) using 0.951 vials (polycarbonate tube, steel end plug and styrol type impactor) as a grinding container and 0.9 g of organic solvent insoluble matter of rubber-containing graft polymer MILL: Condition 15 minutes of precooling, grinding time 2 minutes (20 times / second), cooling time 2 minutes cooling, 4 cycles), precisely weighed 100 mg of the freeze-ground organic solvent insoluble matter, transfer to a 50 mL vial, After adding 30 mL of acetone and stirring, the mixture is allowed to stand for 10 hours, using a centrifuge (Hitachi high speed cooling centrifuge (CR22N), manufactured by Hitachi Koki Co., Ltd.), temperature: 4 ° C., rotation number: 12, Centrifuge at 000 rpm for 60 minutes to separate solubles and insolubles.
- a centrifuge Hitachi high speed cooling centrifuge (CR22N), manufactured by Hitachi Ko
- Acetone (30 mL) is again added to the obtained insoluble matter and dispersed, and the resulting insoluble matter is centrifuged by a centrifuge to separate it into soluble matter and insoluble matter.
- the soluble component and the insoluble component are each dried in an inert oven at 40 ° C. for at least 10 hours. What dried the soluble part among these was made into the organic solvent extract (fw) after freeze-grinding of a rubber containing graft polymer.
- the freeze grinding should be carried out at a ratio not higher than the proportion of components having a glass transition temperature of 60 ° C. or higher in the feed composition of the rubber-containing graft polymer. If the feed composition is unknown, the proportion of components having a glass transition temperature of 60 ° C. or higher in the organic solvent insoluble portion is measured by solid state NMR, and the mixture is pulverized within a range not exceeding it.
- the organic solvent insoluble portion of the rubber-containing graft polymer (A) is further subjected to ozone addition reaction and then extracted by organic solvent extraction.
- the caprolactone unit (CL) is contained in the organic solvent extract (hereinafter referred to as "the organic solvent extract after ozone addition reaction (ow)").
- the diene rubber-containing graft polymer can decompose the rubber-containing graft polymer by ozone addition reaction to selectively take out a crosslinked graft chain.
- the inclusion of the caprolactone unit (CL) means that the caprolactone unit (CL) is included in the graft chain of the rubber-containing graft polymer. .
- a caprolactone unit (CL) By including a caprolactone unit (CL) in the graft chain, it is possible to reduce the dependence of mechanical strength on molding process represented by impact strength.
- the proportion of caprolactone units (CL) is 0.1 to 40 parts by mass with respect to 100 parts by mass of components having a glass transition temperature (Tg) of 60 ° C. or higher contained in the organic solvent extract (ow) after the ozone addition reaction Is preferably 0.5 to 30 parts by mass, and particularly preferably 1.5 to 20 parts by mass. If the ratio of the caprolactone unit (CL) with respect to 100 parts by mass of the component having a glass transition temperature (Tg) of 60 ° C. or higher contained in the organic solvent extract (ow) after the ozone addition reaction is a functional group, Since the groups react with the matrix resin and the rubber is uniformly dispersed in the resin, it is easy to develop excellent mechanical properties.
- the ratio of the caprolactone unit (CL) to the component 100 parts by mass of the glass transition temperature (Tg) contained in the organic solvent extract (ow) after the ozone addition reaction is not more than the above upper limit value, grafting It is easy to suppress that Tg of a component does not become low too much and a subsequent coagulation process becomes difficult.
- the separation (isolation) of the graft chain by the ozone addition reaction of the organic solvent insoluble portion of the diene rubber-containing graft polymer is carried out by the following operations (1) to (9).
- (Ozone addition reaction) (1) 6 mass% of organic solvent insoluble matter of diene rubber containing graft polymer, 94 mass% of 1: 1 mixed liquid of chloroform and methylene chloride is prepared, and it is set as a dispersion. (2) The solution is put into an ozone absorbing bottle and dipped in a dry ice-methanol solution prepared at -60 ° C or less. (3) The ozone gas generated from the ozone generator is blown into an absorption bottle to perform ozone addition.
- the lower layer is drained to a eggplant flask.
- the eggplant flask is set in a constant temperature bath at 65 ° C., and the volatile matter is distilled off by an evaporator.
- the residue in the eggplant flask is vacuum dried at 65 ° C. for 8 hours or more to obtain an organic solvent extract (ow) after the ozone addition reaction of the rubber-containing graft polymer.
- composition analysis of the organic solvent extract after freeze grinding and the organic solvent extract after the ozone addition reaction By subjecting the organic solvent extract (fw) after freeze-pulverization or the organic solvent extract (ow) after ozone addition reaction to pyrolysis GC-MS (gas chromatography mass spectrometer, pyrolysis temperature 500 ° C.) Polymer composition analysis and quantification of caprolactone units (CL) can be made.
- the volume average particle diameter (Dv) of the rubbery polymer that can be used in the present invention is preferably 50 to 400 nm, more preferably 50 to 300 nm, and still more preferably 70 to 250 nm. If the particle size of the rubbery polymer is within the above range, it is easy to make the molded appearance preferable without scattering light, the stress relaxation by the rubber becomes sufficient, and the impact strength also tends to be a sufficient value.
- the volume average particle size can be measured by a nanoparticle size distribution measuring apparatus using a light scattering method or a capillary particle size distribution meter using a CHDF method (Capillary HydroDynamic Fractionation), and it is desirable to measure by a light scattering method.
- the volume average particle diameter of the rubbery polymer can be adjusted by adjusting the amount of the emulsifier in the production of the rubbery polymer by emulsion polymerization.
- the particle size distribution of the rubbery polymer is preferably small, and specifically 1.5 or less.
- the particle size distribution can be quantified by the ratio (Dv / Dn) of the volume average particle size (Dv) to the number average particle size (Dn).
- the particle size distribution can be reduced by adjusting the amount of the emulsifier in the production of the rubbery polymer by emulsion polymerization, and to make the particle size distribution 1.5 or less, the rubbery polymer is prepared by emulsion polymerization. It is preferable to manufacture.
- the volume average particle diameter of the powder containing the rubber-containing graft polymer (A) of the present invention is preferably 300 to 500 ⁇ m. If the particle size of the powder is in the range of 300 to 500 ⁇ m, scattering can be suppressed at the time of compounding or introduction into the mixing apparatus at the time of preparation of the resin composition, which may cause inconveniences such as dust explosion. It is low, and the powder has good flow characteristics, and is less likely to cause problems such as clogging of piping in the manufacturing process.
- Polymerization initiator There is no restriction
- organic peroxides such as t-butylperoxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-hexyl peroxide, etc.
- Oxides or peroxides such as inorganic peroxides such as hydrogen peroxide, potassium persulfate and ammonium persulfate, optionally sodium formaldehyde sulfoxylate, reducing agents such as glucose, and optionally iron sulfate II)
- a redox type polymerization initiator in combination with a transition metal salt such as II, a chelating agent such as disodium ethylenediaminetetraacetate if necessary, and a phosphorus-based flame retardant such as sodium pyrophosphate as required You can also.
- weight average molecular weight (Mw) of the graft chain when it is necessary to control the weight average molecular weight (Mw) of the graft chain, conventional methods such as control of the amount of chain transfer agent and initiator used during polymerization and control of the polymerization temperature can be used.
- chain transfer agents include alkyl mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan.
- the acrylic rubbery polymer ( ⁇ -1) is a (meth) acrylic acid alkyl ester monofunctional monomer ( b-1) (hereinafter referred to as monomer (b-1)) 50 to 100% by mass, monofunctional monomer (b-2) copolymerizable with monomer (b-1) (hereinafter referred to as single monomer Total mass of 100 to 50% by mass of a monomer (b-2) and 0 to 5% by mass of a polyfunctional monomer (b-3) (hereinafter referred to as a monomer (b-3))
- the (meth) acrylic acid alkyl ester type copolymer obtained by using and polymerizing so that it becomes mass% is preferable.
- the monomer (b-1) for example, acrylic acid alkyl ester monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate and the like
- alkyl methacrylate monomers such as hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate and stearyl methacrylate.
- At least one monomer selected from the group consisting of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate is preferable because impact resistance is improved. preferable.
- these can be used alone or in combination of two or more.
- the proportion of the monomer (b-1) in the acrylic rubber-like polymer ( ⁇ -1) (100% by mass) is more preferably 60% by mass to 100% by mass, 70% by mass from the viewpoint of impact resistance. -100% by mass is more preferable, 80% by mass to 98% by mass is particularly preferable, and 90% by mass to 95% by mass is most preferable.
- Examples of the monomer (b-2) include aromatic vinyl monomers such as styrene and ⁇ -methylstyrene, vinyl cyanide monomers such as acrylic acid nitrile and methacrylic acid nitrile, and (meth) acrylic group modified Various vinyl monomers such as silicone can be mentioned.
- the polymerization method of the monomer (b-2) is not particularly limited, and may be charged simultaneously with the monomer (b-1), or may be separately charged with the monomer (b-1). May be
- the proportion of the monomer (b-2) in the acrylic rubber-like polymer ( ⁇ -1) (100% by mass) is more preferably 0% by mass to 40% by mass, and 0% by mass -30% by mass is more preferable, 0% by mass to 20% by mass is particularly preferable, and 0.5% by mass to 5% by mass is most preferable.
- the monomer (b-3) for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, di (meth) acrylic acid 1 And 4-butylene glycol, divinylbenzene, polyfunctional (meth) acrylic group-modified silicone, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. These can be used alone or in combination of two or more.
- the polymerization method of the monomer (b-3) is not particularly limited, but in order to obtain a suitable cross-linked structure, it is mixed with the monomer (b-1) or / and the monomer (b-2), and polymerization is carried out. It is preferable to do.
- the proportion of the monomer (b-3) in the acrylic rubber-like polymer ( ⁇ -1) (100% by mass) is more preferably 0.1% by mass to 4% by mass from the viewpoint of impact resistance, 0 More preferably, 2% by mass to 3% by mass and particularly preferably 0.5% by mass to 2% by mass.
- the rubber-containing graft polymer (A) in which the rubber portion is an acrylic rubber-like polymer ( ⁇ -1) is referred to as an acrylic rubber-containing graft polymer.
- a latex containing a diene rubber-like polymer (diene rubber latex) is obtained, for example, by emulsion polymerization of 1,3-butadiene and one or more vinyl monomers copolymerizable with 1,3-butadiene. Can be manufactured.
- a latex containing a butadiene-based rubbery polymer can be copolymerized with 50 to 100% by mass of 1,3-butadiene in 100% by mass of the total amount of monomers used for producing a diene-based rubbery polymer It consists of a monomer composition of 0 to 50% by mass of one or more vinyl monomers. Furthermore, 60 mass% or more is preferable, and, as for the ratio of 1, 3- butadiene, 65 mass% or more is more preferable. If the proportion of 1,3-butadiene in 100% by mass of the total amount of monomers is equal to or more than the above lower limit value, sufficient impact resistance is easily obtained.
- examples of vinyl monomers include aromatic vinyls such as styrene and ⁇ -methylstyrene, methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate, acrylic acid alkyl esters such as ethyl acrylate and n-butyl acrylate, acrylonitrile Unsaturated nitriles such as methacrylonitrile, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, vinyl chlorides such as vinyl chloride and vinyl bromide, vinylidene halides such as vinylidene chloride and vinylidene bromide, glycidyl acrylate, glycidyl methacrylate, allyl Examples thereof include vinyl monomers having a glycidyl group such as glycidyl ether and ethylene glycol glycidyl ether.
- aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate, trimethacrylates, triacrylates, allyl acrylate, methacrylates
- Crosslinkable monomers such as carboxylic acid allyl esters such as acid allyl, diallyl phthalates, diaryl sebacates, and di- and triallyl compounds such as triallyl triazine may be used in combination.
- the vinyl-based monomer and the crosslinkable monomer may be used alone or in combination of two or more.
- a chain transfer agent such as t-dodecyl mercaptan, n-octyl mercaptan, ⁇ -methyl styrene, etc. can be used when necessary in polymerization of a butadiene rubber polymer.
- an emulsion polymerization method As a polymerization method of a latex containing a butadiene rubber-like polymer, an emulsion polymerization method is used, and the polymerization can be suitably carried out in the range of about 40 to 80 ° C. although it depends on the kind of the polymerization initiator. Moreover, as an emulsifier, a well-known emulsifier can be used suitably. Before the start of polymerization, a seed latex made of, for example, styrene may be pre-charged. As a polymerization method, multistage emulsion polymerization is preferable.
- the monomer composition initially charged and the monomer composition subsequently introduced may be the same or may be changed.
- the rubber-containing graft polymer (A) in which the rubber portion is a diene rubber-like polymer is referred to as a diene rubber-containing graft polymer.
- the polyorganosiloxane rubber-like polymer (Polyorganosiloxane rubber-like polymer) is one or two selected from polyorganosiloxane rubber (S-1) or polyorganosiloxane composite rubber (S-2).
- the polyorganosiloxane rubber (S-1) is an organosiloxane, a grafting agent for polyorganosiloxane (hereinafter also referred to as “siloxane crosslinking agent”), and, if necessary, a crosslinking agent for polyorganosiloxane (hereinafter, “siloxane crosslinking” Obtained by emulsion polymerization of an organosiloxane mixture composed of an “agent” and a siloxane oligomer having an end blocking group.
- the organosiloxane either a chain organosiloxane or a cyclic organosiloxane can be used, but a cyclic organosiloxane is preferable because it has high polymerization stability and high polymerization rate.
- the cyclic organosiloxane is preferably a three- or more-membered cyclic organosiloxane, and more preferably a three- to six-membered ring.
- cyclic organosiloxanes examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclo Tetrasiloxane is mentioned. One of these may be used alone, or two or more may be used in combination.
- siloxane cross-linking agent one capable of forming a bond with the organosiloxane via a siloxane bond and forming a bond with a monomer constituting the poly (meth) acrylic acid ester or a vinyl monomer such as a vinyl monomer preferable.
- a vinyl monomer such as a vinyl monomer preferable.
- alkoxysilane compounds having a vinyl group are preferred.
- a siloxane crosslinking agent it is possible to obtain a polyorganosiloxane having a functional group that can be polymerized with any vinyl copolymer.
- the polyorganosiloxane has a functional group capable of polymerizing with any vinyl monomer, the polyorganosiloxane can be chemically bonded to the poly (meth) acrylic acid alkyl ester or vinyl monomer.
- siloxane crossing agent As a siloxane crossing agent, the siloxane represented by Formula (I) can be mentioned.
- R 1 represents a methyl group, an ethyl group, a propyl group or a phenyl group.
- R 2 represents an organic group in the alkoxy group, and examples thereof include a methyl group, an ethyl group, a propyl group or a phenyl group.
- n is 0, 1 or 2;
- R represents any group represented by formulas (I-1) to (I-4).
- R 3 and R 4 each represent hydrogen or a methyl group, and p represents an integer of 1 to 6.
- a methacryloyloxyalkyl group can be mentioned.
- siloxane having this group for example, ⁇ -methacryloyloxyethyldimethoxymethylsilane, ⁇ -methacryloyloxypropylmethoxydimethylsilane, ⁇ -methacryloyloxypropyldimethoxymethylsilane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxy Mention may be made of propylethoxydiethylsilane, ⁇ -methacryloyloxypropyldiethoxymethylsilane, ⁇ -methacryloyloxybutyldiethoxymethylsilane.
- Examples of the functional group represented by the formula (I-2) include a vinylphenyl group and the like.
- a siloxane which has this group vinylphenylethyl dimethoxysilane can be mentioned, for example.
- Examples of the siloxane having a functional group represented by the formula (I-3) include vinyltrimethoxysilane and vinyltriethoxysilane.
- Examples of the functional group represented by the formula (I-4) include mercaptoalkyl groups.
- Examples of siloxanes having this group include ⁇ -mercaptopropyldimethoxymethylsilane, ⁇ -mercaptopropylmethoxydimethylsilane, ⁇ -mercaptopropyldiethoxymethylsilane, ⁇ -mercaptopropylethoxydimethylsilane, and ⁇ -mercaptopropyltrimethoxysilane. be able to.
- siloxane crosslinking agents may be used alone, or two or more thereof may be used in combination.
- siloxane crosslinking agent what has three or four functional groups which can be couple
- siloxane crosslinking agents include trialkoxyalkylsilanes such as trimethoxymethylsilane; trialkoxyarylsilanes such as triethoxyphenylsilane; tetramethoxysilane such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetrabutoxysilane, etc.
- An alkoxysilane is mentioned. One of these may be used alone, or two or more may be used in combination. Among these, tetraalkoxysilane is preferable, and tetraethoxysilane is more preferable.
- the siloxane oligomer having a terminal blocking group refers to a siloxane oligomer having an alkyl group or the like at the end of the organosiloxane oligomer and stopping the polymerization of the polyorganosiloxane.
- a siloxane oligomer having an end blocking group for example, hexamethyldisiloxane, 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane And methoxytrimethylsilane.
- the content ratio of the organosiloxane in the organosiloxane mixture (100% by mass) is preferably in the range of 60 to 99.9% by mass, and more preferably in the range of 70 to 99.9% by mass.
- the content of the siloxane crossing agent in the organosiloxane mixture (100% by mass) is preferably in the range of 0.1 to 10% by mass.
- the content of the siloxane crosslinking agent in the organosiloxane mixture (100% by mass) is preferably in the range of 0 to 30% by mass.
- the polyorganosiloxane composite rubber (C1-3S-2) includes a polyorganosiloxane rubber (S-1) and a vinyl polymer for composite rubber.
- the polyorganosiloxane composite rubber (S-2) contains a polyorganosiloxane rubber (S-1) and a polyalkyl (meth) acrylate rubber.
- the vinyl polymer for composite rubber is obtained by polymerizing a vinyl monomer for composite rubber and, if necessary, a crosslinkable monomer or an acrylic crosslinking agent.
- Examples of the vinyl monomer for composite rubber include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and the like; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i- And alkyl methacrylates such as butyl methacrylate; aromatic vinyl monomers such as styrene and ⁇ -methylstyrene; and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile.
- n-butyl acrylate is preferable because the impact resistance of the molded article is excellent.
- the crosslinkable monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds.
- the acrylic crosslinking agent is a polyfunctional monomer having two or more polymerizable unsaturated bonds having different reactivity. By having groups having different reactivities, when polymerized together with other components, unsaturated groups are incorporated into the composite rubber in a state of preserving them, which enables formation of a graft copolymer. For example, allyl methacrylate, triallyl cyanurate and triallyl isocyanurate can be mentioned, and these can be used alone or in combination of two or more.
- the acrylic crosslinking agent also has a function as a crosslinking agent since it has two or more polymerizable unsaturated bonds as in the case of the crosslinking monomer.
- the crosslinkable monomer is preferably used in an amount of 0 to 15 parts, more preferably 0.1 to 10 parts, per 100 parts by mass of the composite rubber vinyl monomer. If the amount of use of the crosslinkable monomer is 15 parts or less or less, the impact resistance of the molded article tends to be excellent if the amount is not more than the above-mentioned upper limit value.
- the acrylic crosslinking agent is preferably used in an amount of 0 to 15 parts, more preferably 0.1 to 10 parts, per 100 parts by mass of the composite rubber vinyl monomer. If the use amount of the crosslinkable monomer acrylic crosslinking agent is 15 parts or less or less and the above upper limit value or less, the impact resistance of the molded article tends to be excellent.
- the content of the polyorganosiloxane rubber (S-1) is preferably 0.1% by mass to 99.9% by mass in 100% by mass of the polyorganosiloxane composite rubber (S-2), and is preferably 5% by mass or more 90% by mass is more preferable, and 7% by mass to 85% by mass is particularly preferable. If the content of the polyorganosiloxane rubber (S-1) is at least the lower limit value, the impact resistance of the molded article tends to be excellent. If the content of the polyorganosiloxane rubber (S-1) is equal to or less than the above upper limit value, the heat resistance of the molded article tends to be excellent.
- the rubber-containing graft polymer (A) in which the rubber portion is a polyorganosiloxane rubber-like polymer is referred to as a Si-based rubber-containing graft polymer.
- the rubber-containing graft polymer (A) obtained by the above production method is excellent in the dispersibility of the “rubber-like polymer” in the thermoplastic resin, and the mechanical strength represented by impact strength is improved. In addition, the mechanical strength is improved regardless of the improvement of weld strength and the condition in which the thermoplastic resin is melt-molded by injection molding or the like (the molding dependency is low).
- the emulsifier used for producing the rubber-containing graft polymer (A) is not particularly limited, and, for example, anionic salts such as fatty acid salts, alkyl sulfuric acid ester salts, alkyl benzene sulfonic acid salts, alkyl phosphoric acid ester salts, and dialkyl sulfosuccinates Surfactants; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and glycerin fatty acid esters; and cationic surfactants such as alkylamine salts can be used. Also, these emulsifiers can be used alone or in combination.
- the polymerization method for obtaining the rubber-containing graft polymer (A) can be carried out by emulsion polymerization, and if necessary, forced emulsion polymerization.
- a monomer constituting an acrylic component at the time of polymerization of an acrylic rubber-like polymer ( ⁇ -1) a monomer having poor water solubility such as 2-ethylhexyl acrylate, lauryl methacrylate and stearyl methacrylate is selected
- the rubber-containing graft polymer (A) in the latex state obtained by the graft polymerization of the present invention can be obtained as a powder by coagulation and washing followed by drying or by spray recovery.
- the rubber-containing graft polymer-containing resin composition of the present invention comprises the rubber-containing graft polymer (A) of the present invention and a thermoplastic resin (B).
- thermoplastic resins including polyesters, aromatic polycarbonates, styrenic resins, vinyl chloride resins, olefin resins such as polyethylene, etc. are frequently used as resin modifiers mainly composed of methyl methacrylate.
- a rubber-containing graft polymer (A) having a graft chain mainly composed of methyl methacrylate can be suitably used.
- thermoplastic resin is not particularly limited, and can be applied to various resins such as engineering plastics, styrene resins, polyesters, olefin resins, thermoplastic elastomers, biodegradable polymers, halogen polymers, acrylic resins and the like.
- the engineering plastics are not particularly limited as long as they are known various thermoplastic engineering plastics, and polyester polymers such as polyphenylene ether, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, syndiotactic polystyrene, 6-nylon, 6,6 -Examples of nylon polymers such as nylon, polyarylates, polyphenylene sulfide, polyether ketones, polyether ether ketones, polysulfones, polyether sulfones, polyamide imides, polyether imides, poly acetals and the like.
- polyester polymers such as polyphenylene ether, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, syndiotactic polystyrene, 6-nylon, 6,6 -Examples of nylon polymers such as nylon, polyarylates, polyphenylene sulfide, polyether ketones, polyether ether ketones, polysulfone
- aromatic polycarbonates aromatic polycarbonates, polyesters and styrenic resins for which strength development is required are more preferable.
- the aromatic polycarbonate is not particularly limited as long as it is a polymer compound having a carbonic ester bond (—O—C (O) —O—) in the main chain.
- Examples include 4,4'-dioxydiarylalkane polycarbonates such as 2,2-bis (4-hydroxyphenyl) propane polycarbonate (bisphenol A polycarbonate).
- olefin resin high density polyethylene, medium density polyethylene, low density polyethylene, copolymer of ethylene and other ⁇ -olefins; polypropylene, copolymer of propylene and other ⁇ -olefins; polybutene, poly- 4-methylpentene-1 and the like.
- styrene-butadiene-styrene copolymer SBS
- styrene-isoprene-styrene copolymer SIS
- SEB styrene-ethylene-butene copolymer
- SEP styrene-ethylene-propylene copolymer
- SEBS styrene-ethylene-propylene-styrene copolymer
- SEPS styrene-ethylene-propylene-styrene copolymer
- SEEPS styrene-ethylene-ethylene-propylene-styrene copolymer
- SEEPS styrene Butadiene-butylene-styrene copolymer
- SBBS partially hydrogenated product of styrene-isoprene-styrene copolymer
- styrene resin polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene- ⁇ -methylstyrene copolymer, acrylonitrile-methyl methacrylate-styrene- ⁇ -methylstyrene copolymer, ABS resin, AS resin, MABS resin , MBS resin, AAS resin, AES resin, acrylonitrile-butadiene-styrene- ⁇ -methylstyrene copolymer, acrylonitrile-methyl methacrylate-butadiene-styrene- ⁇ -methylstyrene copolymer, styrene-maleic anhydride copolymer, Styrene-maleimide copolymer, styrene-N-substituted maleimide copolymer, acrylonitrile-styrene-N-substituted maleimide copolymer,
- the polyester is a polymer composed of a polybasic acid and a polyhydric alcohol, and is not particularly limited as long as it has thermoplasticity.
- polybasic acids include terephthalic acid, naphthaldicarboxylic acid, cyclohexyldicarboxylic acid or esters thereof, and polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexane Diol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis (4-hydroxyethoxyphenyl) propane, 1,4-dimethylol tetrabromobenzene, TBA-EO and the like.
- the polyester resin may be a homopolymer, a copolymer, or a blend of two or more of these.
- biodegradable polymers examples include microbial polymers such as biopolyesters (PHB / V etc.), bacterial cellulose, microbial polysaccharides (pullulan, curdlan etc.), and aliphatic polyesters (polycaprolactone, polybutylene succinate, polyethylene succinate) And chemically synthesized polymers such as polyglycolic acid and polylactic acid), polyvinyl alcohol, polyamino acids (PMLG and the like), and natural products based polymers such as chitosan / cellulose, starch and cellulose acetate.
- microbial polymers such as biopolyesters (PHB / V etc.), bacterial cellulose, microbial polysaccharides (pullulan, curdlan etc.), and aliphatic polyesters (polycaprolactone, polybutylene succinate, polyethylene succinate)
- chemically synthesized polymers such as polyglycolic acid and polylactic acid), polyvinyl alcohol, polyamino acids
- the halogenated polymer may, for example, be a homopolymer of vinyl chloride, a copolymer containing 80% by mass or more of vinyl chloride, and highly chlorinated polyvinyl chloride.
- As components of the copolymer besides vinyl chloride, monovinyl compounds such as ethylene, vinyl acetate, methyl methacrylate and butyl acrylate can be mentioned. These monovinyl compounds may be contained in a total amount of 20% by mass or less in 100% by mass of the copolymer.
- the homopolymers and copolymers may be contained singly or in combination of two or more.
- a fluorinated polymer, a brominated polymer, an iodinated polymer etc. are mentioned.
- acrylic resins include copolymers obtained by polymerizing vinyl monomers copolymerizable with methyl methacrylate.
- vinyl monomers copolymerizable with the above methyl methacrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl
- alkyl methacrylates such as methacrylate
- aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and vinyl toluene.
- Polyester resins such as polyphenylene ether, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, syndiotactic polystyrene, polyamide resins such as 6-nylon and 6,6-nylon, polyarylate, polyphenylene sulfide, polyether ketone, polyether ether
- polymer alloys of engineering plastics such as ketones, polysulfones, polyethersulfones, polyamideimides, polyetherimides, polyacetals and the like and the above-mentioned thermoplastic resins.
- the resin composition of the present invention is, in addition to the above-mentioned materials, known various additives such as stabilizers, flame retardants, flame retardant assistants, hydrolysis inhibitors, charging, as long as the object of the present invention is not impaired. It can contain an inhibitor, a blowing agent, a dye, a pigment and the like.
- a well-known blending method is mentioned, It does not specifically limit.
- mixing roll, an extruder etc. is mentioned.
- Production Examples 1 to 13 are production examples of a rubbery polymer, a rubber-containing graft polymer (A) and the like.
- part means “mass part”
- % means “mass%.”
- the rubber-forming monomer “component 4” shown in Table 1 was forcibly emulsified, and was dropped into the separable flask while controlling the liquid temperature at 80 ⁇ 2 ° C. over 180 minutes. Thereafter, the solution temperature was kept at 80 ° C. ⁇ 2 ° C. for 60 minutes. Thus, a latex of a rubbery polymer was obtained. The particle diameter of the rubbery polymer latex at this time was 230 nm as a result of measurement by the light scattering method. The polymerization rate was 99%. Subsequently, while the temperature of the graft component monomer “component 5” shown in Table 1 was controlled at 80 ⁇ 2 ° C., it was added dropwise over 30 minutes.
- sodium dodecyl benzene sulfonate is a trade name "Neoperex G-15, manufactured by KAO (16% aqueous solution of sodium dodecyl benzene sulfonate)
- sodium dialkyl sulfosuccinate is a trade name "Perex OT-P, manufactured by KAO ( (Dialkylsulfosuccinate 80% methanol solution) was used.
- An aqueous solution containing “component 6” shown in Table 2 was set to a temperature of 40 ° C. ⁇ 5 ° C., and an acrylic rubber graft latex was charged into the aqueous solution to form a slurry.
- the slurry was coagulated by raising the liquid temperature to 70 ° C. ⁇ 5 and holding for 5 minutes.
- the process of collecting the aggregate, soaking in 1500 parts of deionized water and dewatering was repeated twice and dried at a temperature of 65 ° C. ⁇ 5 for 12 hours to obtain a powder of a rubber-containing graft polymer (A-1) .
- the polymerization initiator of “component 9” shown in Table 3 is added, and 1 hour after that, the second monomer mixed liquid of “component 10” shown in Table 3 and “Component shown in Table 3
- the emulsifier aqueous solution of 11 "and the polymerization initiator of" component 12 "shown in Table 3 were continuously dripped in the autoclave over 8 hours. The reaction was allowed to proceed for 4 hours from the initiation of polymerization to obtain a latex (R-1) of a rubbery polymer.
- the mixture of “component 14” shown in Table 4 was forcedly emulsified, dropped into the reaction vessel over 60 minutes, and then heating and stirring were continued for 120 minutes.
- the vinyl monomer was graft polymerized to the rubbery polymer to obtain a latex of the rubber-containing graft polymer.
- the polymerization rate was 100%.
- the sodium alkyl diphenyl ether disulfonate used was sodium dodecyl benzene sulfonate, under the trade name "Neoperex G-15, manufactured by KAO (16% aqueous solution of sodium dodecyl benzene sulfonate)".
- the unsaturated fatty acid hydroxyalkyl ester-modified ⁇ -caprolactone is represented by the above general formula (3), and the trade name “Placel FM1” (manufactured by Daicel Corporation) was used.
- a powder of a rubber-containing graft polymer (B-6, 7) was obtained in the same manner as in Production Example 7 except that each component shown in Table 4 was changed, and "Component 14" shown in Table 4 was not forcedly emulsified.
- the polymerization rate was 100%.
- TEOS tetraethoxysilane
- DSMA methacryloyloxypropyl dimethoxymethylsilane
- n-BA n-butyl acrylate
- AMA allyl methacrylate
- t-BH tert-butyl hydroperoxide
- MMA methyl methacrylate
- unsaturated fatty acid hydroxyalkyl ester modified ⁇ -caprolactone 10 parts
- sodium dodecylbenzene sulfonate 10 parts
- t-BH sodium dodecylbenzene sulfonate
- the liquid temperature was maintained at 65 ° C. for 1 hour, and then cooled to 25 ° C. to obtain a latex of the rubber-containing graft polymer (A-5).
- a trade name “Placel FM1” (manufactured by Daicel Corporation) represented by the above general formula (3) was used.
- the obtained rubber-containing graft polymer (A-5) latex is added to 300 parts by mass of deionized water containing 5 parts by mass of calcium acetate to coagulate the polymer, washed with water, dehydrated and dried to give a rubbery product A powder of graft polymer (A-5) was obtained.
- Production Example 13 While maintaining the temperature of the polyorganosiloxane / n-BA composite rubber latex (S-3) prepared in the same manner as in Production Example 12 at 65 ° C., 27.7 parts of n-BA and 0 of AMA A mixture of 0.1 part of 3 parts of t-BH was dropped into this latex over 45 minutes, and the mixture was heated and stirred for 1 hour. Then, a mixed solution of 10.5 parts of methyl methacrylate (MMA), 0.5 parts of n-BA and 0.06 parts of t-BH was dropped into this latex for 20 minutes and polymerized. After completion of the dropwise addition, the liquid temperature was maintained at 65 ° C. for 1 hour, and then cooled to 25 ° C. to obtain a latex of rubber-containing graft polymer (B-8).
- S-3 polyorganosiloxane / n-BA composite rubber latex
- the obtained rubber-containing graft polymer (B-8) latex is added to 300 parts by mass of deionized water containing 5 parts by mass of calcium acetate to coagulate the polymer, washed with water, dehydrated and dried to give a rubber A powder of graft polymer (B-8) was obtained.
- the organic solvent insoluble fraction is calculated from the mass of the dry sample of the organic solvent insoluble fraction obtained in the above operation (9). The value obtained by subtracting the mass of the organic solvent insoluble matter from the preparation mass of the rubber-containing graft polymer is the organic solvent soluble matter.
- a reducing agent sodium borohydride
- a methanol 90% by mass solution in a beaker is stirred with a magnetic stirrer. After dissolution, add (4) Absorbent solution and stir for 3 hours or more.
- the eggplant flask is set in a constant temperature bath at 65 ° C., and the volatile matter is distilled off by an evaporator. (9) The residue in the eggplant flask is vacuum dried at 65 ° C. for 8 hours or more to obtain a “graft chain dried sample”.
- caprolactone unit (CL) It analyzed according to the procedure of the following (1) and (2).
- the “grafted chain dry sample” obtained by the operation of the above [1] is subjected to pyrolysis GC-MS (gas chromatography mass spectrometry) at 500 ° C. under the conditions shown in 1) to 4) below. It was thermally decomposed and the polymer composition ratio of the graft chain was measured.
- the standard polymer was prepared by emulsion polymerization, and the polymerization rate was 99% or more.
- the mass ratio of CL in the standard polymer is calculated from the molar mass (244.3 g / mol) of the unsaturated fatty acid hydroxyalkyl ester-modified ⁇ -caprolactone and the molar mass of ⁇ -caprolactone (114.1 g / mol).
- a calibration curve showing the ratio of and CL was prepared. The correlation coefficient of the calibration curve was 0.99.
- the mass ratio of CL to 100 parts by mass of MMA in each sample was calculated using a calibration curve, and is shown in Tables 8 to 10.
- Measurement of particle size was carried out using a nanoparticle size distribution measuring device SALD-7100 (manufactured by Shimadzu Corporation).
- the polymerization rate of the graft latex is measured by the following procedure.
- Examples 1 to 5 Comparative Examples 1 to 7
- the rubber-containing graft polymer (A-1) obtained in Production Example 1 and a polybutylene terephthalate resin ("Novadurane 5010R5" (trade name) were blended according to the composition shown in Table 5 and mixed to obtain a mixture.
- the mixture is supplied to a volatilization type twin-screw extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) heated to a barrel temperature of 260 ° C. and kneaded, and 15 mass% of rubber-containing graft polymer (A-1) is blended. Pellets of the resin composition of Example 1 were produced.
- PCM-30 volatilization type twin-screw extruder
- Examples 2 to 9 and Comparative Example were the same as Example 1 except that the type and / or amount of use of the rubber-containing graft polymer and the blending amounts of the other raw materials were changed to the conditions shown in Tables 5 to 7. Pellets of each resin composition of Examples 1 to 12 were prepared.
- PBT polybutylene terephthalate resin
- PC polybutylene terephthalate resin
- aromatic polycarbonate (“Iupilon S-2000F” (trade name), manufactured by Mitsubishi Engineering Plastics Co., Ltd., nominal) Mv of aromatic polycarbonate resin: 22000), Styrene acrylonitrile resin (SAN), SAN-based resin “AP-H” (trade name), Techno UMG Co., Ltd., nominal AN ratio is around 26%, Mw about 110,000 )It was used.
- the weld strength in the evaluation of the present invention is defined as the breaking elongation of the tensile test of the test piece shown in FIG. 1b.
- test piece is immersed in a 2.0% by mass aqueous solution of osmium tetroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and stained at 25 ° C. for 12 hours, and then the thickness of a thin plate is 50 nm and the cutting speed is 0
- a slice was cut out under the conditions of 4 mm / sec and collected on a copper foil with a supporting film. The thin sections collected on the grid are stained at 25 ° C.
- PBT Polybutylene terephthalate resin ("Novaduran (registered trademark) 5010 R5")
- Ac-CL unsaturated fatty acid hydroxyalkyl ester modified ⁇ -caprolactone (registered trademark) “Placel FM-1” (manufactured by Daicel)
- CL caprolactone unit MMA: methyl methacrylate
- GMA glycidyl methacrylate
- PBT Polybutylene terephthalate resin (registered trademark "Novaduran 5010R5")
- PC Aromatic polycarbonate resin ((R) "Yupilon S-2000F")
- Ac-CL unsaturated fatty acid hydroxyalkyl ester modified ⁇ -caprolactone (registered trademark) “Placel FM-1” (manufactured by Daicel)
- CL caprolactone unit
- MMA methyl methacrylate
- GMA glycidyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- SAN Styrene acrylonitrile resin
- PC Aromatic polycarbonate resin ((R) "Yupilon S-2000F")
- Ac-CL unsaturated fatty acid hydroxyalkyl ester modified ⁇ -caprolactone (registered trademark) “Placel FM-1” (manufactured by Daicel)
- CL caprolactone unit
- MMA methyl methacrylate
- St-AN copolymer of styrene and acrylonitrile
- the rubber-containing graft polymer (A) of the present invention contains a caprolactone unit (CL) derived from the unsaturated fatty acid hydroxyalkyl ester modified ⁇ -caprolactone represented by the general formula (3).
- a rubber-containing graft polymer (A) having a caprolactone unit (CL) in the graft chain as compared with the rubber-containing graft polymer (B-4) having 2-hydroxyethyl methacrylate (A) -1) showed superiority in weld strength. This is considered to be due to the difference in the reactivity of the hydroxyl group present at the side chain end of the graft chain.
- the terminal hydroxyl group derived from the unsaturated fatty acid hydroxyalkyl ester modified ⁇ -caprolactone is present at a position separated from the main chain skeleton,
- the hydroxyl group of 2-hydroxyethyl methacrylate is considered to be less reactive because it is located near the main chain skeleton of the graft chain.
- the TEM observation results of the resin obtained in Example 8 and Comparative Example 10 are summarized in FIG.
- the sea is an aromatic polycarbonate
- the island is a phase diagram of a styrene acrylonitrile resin, which indicates which phase the black-colored, circular rubber is disposed.
- the rubber derived from the rubber-containing graft polymer (B-6) in the resin composition obtained in Comparative Example 10 is localized at the phase interface between the aromatic polycarbonate and the styrene acrylonitrile resin, while Example 8
- the rubber derived from the rubber-containing graft polymer (A-4) in the resin composition obtained in the above is uniformly dispersed in the matrix resin.
- Example 8 was superior in low temperature impact strength, so it can be said that the impact strength is improved as the rubber is uniformly dispersed.
- the rubber in FIG. 3 to Example 8 is uniformly dispersed, and is present on the aromatic polycarbonate side.
- phase separation derived from styrene acrylonitrile resin is also finely and uniformly dispersed. Since aromatic polycarbonates are softer than styrene acrylonitrile resins, it is believed that deformation of the aromatic polycarbonates first occurs when stress is applied.
- the rubber be uniformly dispersed and present on the aromatic polycarbonate side in that the volume strain caused by the deformation is relieved by the cavitation of the rubber.
- the phase separation derived from styrene acrylonitrile resin is also fine and uniformly dispersed, it is considered that both of the impact strengths are high.
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Abstract
Description
本願は、2017年12月25日に、日本出願された特願2017-247766号に基づき優先権を主張し、その内容をここに援用する。
しかし、グラフト鎖がメチルメタクリレートの場合、樹脂中でのゴムの分散が不十分なため、低温衝撃強度やウェルド強度は満足できるものではない。
しかし、エポキシ基により、熱可塑性樹脂またはゴム含有グラフト重合体での架橋が生じるため、エポキシ基量により流動性が低下することがある。また、エポキシ基量を調整しても十分満足できる機械的強度(衝撃強度・ウェルド強度等)を得ることができていない。
このゴム含有グラフト重合体を、ポリカーボネート樹脂やポリエステル樹脂といったエステル結合を有する熱可塑性樹脂に配合した場合、グラフト鎖のヒドロキシ基がエステル結合部分と化学反応を伴う共有結合が形成され、樹脂中にゴムを均一に分散する可能性があるが、ウェルド強度の向上には至っていない。
本発明は、以下の態様を有する。
前記ゴム含有グラフト重合体を有機溶剤と混合して、有機溶剤不溶分と有機溶剤可溶分に分離させたとき、前記有機溶剤不溶分に含まれるグラフト鎖中にカプロラクトン単位を含むゴム含有グラフト重合体。
[2]前記有機溶剤不溶分のグラフト鎖中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.1~40質量部含む、[1]に記載のゴム含有グラフト重合体。
[3]前記有機溶剤不溶分のグラフト鎖中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.5~30質量部含む、[2]に記載のゴム含有グラフト重合体。
[4]前記有機溶剤不溶分のグラフト鎖中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を1.5~20質量部含む、[3]に記載のゴム含有グラフト重合体。
[5]前記有機溶剤不溶分に凍結粉砕を施し、凍結粉砕された有機溶剤不溶分を有機溶剤と混合して、凍結粉砕後の有機溶剤不溶分と凍結粉砕後の有機溶剤抽出物に分離させたとき、前記凍結粉砕後の有機溶剤抽出物にカプロラクトン単位を含む、[1]に記載のゴム含有グラフト重合体。
[6]前記凍結粉砕後の有機溶剤抽出物に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.1~40質量部含む、[5]に記載のゴム含有グラフト重合体。
[7]前記凍結粉砕後の有機溶剤抽出物に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.5~30質量部含む、[6]に記載のゴム含有グラフト重合体。
[8]前記凍結粉砕後の有機溶剤抽出物に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を1.5~20質量部含む、[7]に記載のゴム含有グラフト重合体。
[9]前記有機溶剤不溶分にオゾン付加反応を施し、オゾン付加された有機溶剤不溶分を有機溶剤と混合して、オゾン付加反応後の有機溶剤不溶分とオゾン付加反応後の有機溶剤抽出物に分離させたとき、前記オゾン付加反応後の有機溶剤抽出物に、カプロラクトン単位を含む、[1]に記載のゴム含有グラフト重合体。
[10]前記オゾン付加反応後の有機溶剤抽出物中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.1~40質量部含む、[9]に記載のゴム含有グラフト重合体。
[11]前記オゾン付加反応後の有機溶剤抽出物中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.5~30質量部含む、[10]に記載のゴム含有グラフト重合体。
[12]前記オゾン付加反応後の有機溶剤抽出物中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を1.5~20質量部含む、[11]に記載のゴム含有グラフト重合体。
[13]ゴムラテックス50~95質量%に、下記一般式(1)で表されるビニル単量体(f-1)を含むグラフト用単量体(b)5~50質量%を乳化グラフト重合させて得られるグラフト重合体。
CH2=CR1COO(CH2)qO[CO(CH2)mO]nH ・・・(1)
(式中、R1は水素またはメチル基を表し、qは2~5、mは3~10、nは1~10の整数を表す)。
[14]前記ビニル単量体(f-1)が、下記一般式(2)で表されるビニル単量体(f-2)である[13]に記載のゴム含有グラフト重合体。
CH2=CR2COO(CH2)qO[CO(CH2)5O]nH ・・・(2)
(式中、R2は水素またはメチル基を表し、qは2~5、nは1~5の整数を表す)。
[15]グラフト用単量体(b)がメチルメタクリレートを含む、[13]または[14]に記載のゴム含有グラフト重合体。
[16]前記ゴム含有グラフト重合体(100質量%)中、前記ビニル単量体(f-1)を0.5~50質量%含む、[13]~[15]のいずれかに記載のゴム含有グラフト重合体。
[17]グラフトさせるゴムの粒子径が50~400nmである、[1]~[16]のいずれかに記載のゴム含有グラフト重合体。
[18][1]~[17]のいずれかに記載のゴム含有グラフト重合体および熱可塑性樹脂(B)を含む、ゴム含有グラフト重合体含有樹脂組成物。
[19]前記熱可塑性樹脂(B)がポリエステル樹脂である、[18]に記載のゴム含有グラフト重合体含有樹脂組成物。
[20]前記熱可塑性樹脂(B)が芳香族ポリカーボネート樹脂とポリエステル樹脂のアロイである、[18]に記載のゴム含有グラフト重合体含有樹脂組成物。
[21]前記熱可塑性樹脂(B)が芳香族ポリカーボネート樹脂とスチレン系樹脂のアロイである、[18]に記載のゴム含有グラフト重合体含有樹脂組成物。
[22][18]~[21]のいずれかに記載のゴム含有グラフト重合体含有樹脂組成物を成形してなる成形体。
[23]射出成形体である、[22]に記載の成形体。
本発明のゴム含有グラフト重合体含有樹脂組成物は、本発明のゴム含有グラフト重合体を含むため、ゴム含有グラフト重合体を樹脂組成物中に均一に分散させることができ、本発明のゴム含有グラフト重合体含有樹脂組成物を成形してなる本発明の成形体は機械的強度に優れる。
[ゴム含有グラフト重合体(A)]
本発明のゴム含有グラフト重合体(以下、「ゴム含有グラフト重合体(A)」とも言う。)は、ゴム状重合体(ゴムラテックス)に対して、ビニル単量体がグラフト重合されたもの(グラフトラテックス)である。
たとえば、乳化剤存在下、水媒体中で得られるゴム状重合体に対してグラフト用単量体(b)がグラフト重合されたものであり、乳化重合により製造されうる。
本発明に用いることができるゴム状重合体としては、ガラス転移温度が0℃以下のものを用いることができる。
ゴム状重合体のガラス転移温度が0℃以下であれば、本発明の樹脂組成物から得られる成形体のシャルピー衝撃試験の値で表される衝撃強度が改善される。
ブタジエンゴム、スチレン・ブタジエン共重合ゴム、シリコーンゴム、シリコーン・アクリル複合ゴム(ジメチルシロキサンを主体とする単量体から得られるゴム状重合体の存在下に、アクリレートを含むビニル単量体の1種または2種以上を重合させて得られるもの)、アクリロニトリル・ブタジエン共重合ゴム、ポリアクリル酸ブチル等のアクリル系ゴム、ポリイソプレン、ポリクロロプレン、エチレン・プロピレンゴム、エチレン・プロピレン・ジエン三元共重合ゴム、スチレン・ブタジエンブロック共重合ゴム、スチレン・イソプレンブロック共重合ゴム等のブロック共重合体、およびそれらの水素添加物等。
ゴム含有グラフト重合体の熱可塑性樹脂に対する分散性は、グラフト鎖の組成によって大きく異なる。
以下、ゴム含有グラフト重合体(A)を構成する、グラフト重合に由来する成分(グラフト用単量体(b)がゴム状重合体にグラフト重合されて形成された成分)を「グラフト成分」とも言う。
前記開環ラクトン部位を有するビニル単量体は、下記一般式(1)で表されるビニル単量(f-1)が好ましい。
CH2=CR1COO(CH2)qO[CO(CH2)mO]nH ・・・(1)
(式中、R1は水素またはメチル基を表し、qは2~5、mは3~10、nは1~10の整数を表す。)
CH2=CR2COO(CH2)qO[CO(CH2)5O]nH ・・・(2)
(式中、R2は水素またはメチル基を表し、qは2~5、nは1~5の整数を表す。)。
前記一般式(2)で示されるビニル単量体(f-2)は、水酸基含有重合性不飽和単量体とε-カプロラクトンとの付加反応によって得られる。
qとしては、2~3の整数であることが好ましく、2がより好ましい。
グラフト重合に供されるグラフト用単量体(b)は、実際にゴム状重合体に化学結合する「ビニル単量体mgp」と、ゴム状重合体に化学結合せずに、重合して、遊離重合体を生成する「ビニル単量体mfp」および重合反応しない「ビニル単量体mfm」に分類することができる。ゴム状重合体と化学結合するビニル単量体mgpのうち、架橋し有機溶剤に不溶の成分「ゴム架橋成分」と化学結合するグラフト用ビニル単量体を本発明の「グラフト鎖」と定義する(後述する「Rg」におけるグラフト鎖)。ビニル単量体mgpにおいて、架橋し有機溶剤に不溶の成分「ゴム架橋成分」と化学結合するビニル単量体の含有割合が多いほうが好ましい。
重合反応しないビニル単量体mfmは、その後の回収工程(後述する凝析または噴霧回収工程と得られた粉の乾燥工程)で、ほぼすべて取り除かれる。
Rg:ゴム架橋成分と、それに化学結合しているグラフト用単量体(b)に由来するグラフト鎖
R0:ゴム架橋成分でグラフトしていないもの
Ng:ゴム非架橋成分と、それに化学結合しているグラフト用単量体(b)に由来するグラフト鎖
N0:ゴム非架橋成分でグラフトしていないもの
「遊離重合体Pf」:ゴム状重合体とグラフトしていないグラフト用単量体(b)に由来する重合物もしくは共重合物
有機溶剤不溶分と有機溶剤可溶分に分離する際に用いることができる有機溶剤は、ゴム含有グラフト重合体(A)を化学的に変質させないもので、かつ、ゴム含有グラフト重合体(A)を構成する非架橋の場合の各ポリマーに対する十分な溶解性があれば特に限定されない。好ましくは、アセトンおよびテトラヒドロフランを挙げることができる。
作業性の観点から、アセトンは揮発性が高く溶剤留去がしやすい点で好ましい。ただし、アセトンはスチレン主成分のポリマーに対して溶解性が低いので、ゴム含有グラフト重合体(A)にスチレン由来の構成単位が含まれる場合はテトラヒドロフランが好ましい。
ゴム含有グラフト重合体(A)の有機溶剤不溶分は、精秤したゴム含有グラフト重合体サンプルと有機溶剤とを十分に混合し、静置した後、遠心分離して有機溶剤可溶分と有機溶剤不溶分とを分離する操作を複数回行い、合わせた有機溶剤不溶分から有機溶媒を除去することで定量することができる。
アセトン不溶分(質量%)=([W1]/[W0])×100
ゴム含有グラフト重合体(A)の有機溶剤不溶分を凍結粉砕することによって、ゴム含有グラフト重合体(A)を分解し、架橋されているグラフト鎖を優先的に取り出すことができる。凍結粉砕によって、架橋されているグラフト鎖および架橋されているゴムの一部が有機溶剤で抽出される。つまり、凍結粉砕後の有機溶剤抽出物(fw)において、カプロラクトン単位(CL)が含まれるということは、ゴム含有グラフト重合体(A)のグラフト鎖に、カプロラクトン単位(CL)が含まれることを意味する。グラフト鎖にカプロラクトン単位(CL)が含まれることによって、衝撃強度に代表される機械的強度の成形加工依存性が低くできる。
凍結粉砕後の有機溶剤抽出物(fw)に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対する、カプロラクトン単位(CL)の割合が前記下限値以上であれば、官能基がマトリクス樹脂と反応してゴムが樹脂中に均一に分散するため、優れた機械的物性を発現しやすい。凍結粉砕後の有機溶剤抽出物(fw)に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対する、カプロラクトン単位(CL)の割合が前記上限値以下であれば、グラフト成分のTgが低くなりすぎず、その後の凝析工程が困難になることを抑制しやすい。
これらのうちの可溶分を乾燥させたものを、ゴム含有グラフト重合体の凍結粉砕後の有機溶剤抽出物(fw)とした。なお、凍結粉砕は、ゴム含有グラフト重合体の仕込み組成におけるガラス転移温度が60℃以上の成分の割合以下の割合で粉砕しなければならない。仕込み組成が不明な場合は、固体NMRによって、有機溶剤不溶分中のガラス転移温度が60℃以上の成分の割合を測定し、それを超えない範囲で粉砕する。
ジエン系ゴム含有グラフト重合体は、オゾン付加反応によって、ゴム含有グラフト重合体を分解し、架橋されているグラフト鎖を選択的に取り出すことができる。つまり、オゾン付加反応後の有機溶剤抽出物(ow)において、カプロラクトン単位(CL)が含まれるということは、ゴム含有グラフト重合体のグラフト鎖に、カプロラクトン単位(CL)が含まれることを意味する。グラフト鎖にカプロラクトン単位(CL)が含まれることによって、衝撃強度に代表される機械的強度の成形加工依存性が低くできる。
オゾン付加反応後の有機溶剤抽出物(ow)に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対する、カプロラクトン単位(CL)の割合が前記下限値以上であれば、官能基がマトリクス樹脂と反応してゴムが樹脂中に均一に分散するため、優れた機械的物性を発現しやすい。オゾン付加反応後の有機溶剤抽出物(ow)に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対する、カプロラクトン単位(CL)の割合が前記上限値以下であれば、グラフト成分のTgが低くなりすぎず、その後の凝析工程が困難になることを抑制しやすい。
(オゾン付加反応)
(1)ジエン系ゴム含有グラフト重合体の有機溶剤不溶分を6質量%、クロロホルムと塩化メチレンとの1:1混合液94質量%を調製し分散溶液とする。
(2)前記溶液をオゾン吸収ビンに入れ、-60℃以下に調製したドライアイス-メタノール溶液に漬ける。
(3)オゾン発生装置より発生したオゾンガスを吸収ビンに吹き込みオゾン付加を行う。
(4)オゾン付加後(吸収液が青色になる)、エアーを吹き込み過剰なオゾンを取り除く。
(5)ビーカーに還元剤(水素化ほう素ナトリウム)を10質量%、メタノール90質量%溶液に調整し、マグネチックスターラーで撹拌する。溶解後、(4)吸収液を入れ3時間以上撹拌する。
(6)撹拌後、(5)の溶液に、(5)溶液の質量の1/5に相当する質量の塩酸水溶液(1:1=塩酸:水)を加えて、3時間以上撹拌する。
(7)撹拌後、分液ロートに移し2層分離させる。この下層をナスフラスコに抜液する。
(8)ナスフラスコを65℃の恒温槽中にセットして、エバポレータによって揮発分を留去する。
(9)ナスフラスコ内の残存物を65℃で8時間以上真空乾燥して、ゴム含有グラフト重合体のオゾン付加反応後の有機溶剤抽出物(ow)を得る。
凍結粉砕後の有機溶剤抽出物(fw)またはオゾン付加反応後の有機溶剤抽出物(ow)を、熱分解GC-MS(ガスクロマトグラフィー質量分析計、熱分解温度500℃)に供することで、ポリマー組成分析およびカプロラクトン単位(CL)の定量をすることができる。
ゴム状重合体の粒子径が前記範囲内にあれば、光を散乱させず成形外観を好ましいものにしやすく、ゴムによる応力緩和が十分となり、衝撃強度も十分な値としやすい。
ゴム状重合体の体積平均粒子径は、乳化重合によるゴム状重合体の製造において、乳化剤の量を調整することにより調整することができる。
粒子径分布は、乳化重合によるゴム状重合体の製造において、乳化剤の量を調整することにより小さくすることができ、粒子径分布を1.5以下とするには乳化重合によりゴム状重合体を製造することが好ましい。
粉体の粒子径が300~500μmの範囲にあれば、樹脂組成物を調製する際の、配合時や混合装置内への投入時に、飛散を抑制でき、粉じん爆発等の不都合を生じさせるおそれが低く、さらに粉の流動特性が良好であり、製造工程での配管の詰まり等の不都合を生じさせにくい。
本発明のゴム含有グラフト重合体のグラフト重合の際に使用される重合開始剤としては、特に制限がなく、公知のものが使用できる。すなわち、2,2’-アゾビスイソブチロニトリル、過酸化水素、過硫酸カリウム、過硫酸アンモニウム等の熱分解型重合開始剤を用いることができる。また、t-ブチルパーオキシイソプロピルカーボネート、パラメンタンハイドロパーオキサイド、クメンハイドロパーオキサイド、ジクミルパーオキサイド、t-ブチルハイドロパーオキサイド、ジ-t-ブチルパーオキサイド、t-ヘキシルパーオキサイド等の有機過酸化物、もしくは過酸化水素、過硫酸カリウム、過硫酸アンモニウム等の無機過酸化物といった過酸化物と、必要に応じてナトリウムホルムアルデヒドスルホキシレート、グルコース等の還元剤、および必要に応じて硫酸鉄(II)等の遷移金属塩、さらに必要に応じてエチレンジアミン四酢酸二ナトリウム等のキレート剤、さらに必要に応じてピロリン酸ナトリウム等のリン系難燃剤等を併用したレドックス型重合開始剤として使用することもできる。
本発明のゴム含有グラフト重合体(A)に用いるゴム状重合体がアクリル系ゴムの場合、アクリル系ゴム状重合体(β-1)は、(メタ)アクリル酸アルキルエステル単官能単量体(b-1)(以下、単量体(b-1)という)50~100質量%、単量体(b-1)と共重合し得る単官能単量体(b-2)(以下、単量体(b-2)という)0~50質量%、および多官能単量体(b-3)(以下、単量体(b-3)という)0~5質量%を、合計質量が100質量%となるように用いて重合して得られる(メタ)アクリル酸アルキルエステル系共重合体が好ましい。
これらは単独または2種以上を併用して用いることができる。
これらは単独または2種以上を併用して用いることができる。
単量体(b-3)の重合方法は特に限定されないが、適切な架橋構造を得るために、単量体(b-1)または/および単量体(b-2)と混合し、重合することが好ましい。
以下、ゴム部がアクリル系ゴム状重合体(β―1)である、ゴム含有グラフト重合体(A)を、アクリル系ゴム含有グラフト重合体と呼ぶ。
ジエン系ゴム状重合体(ジエン系ゴムラテックス)を含有するラテックスは、たとえば、1,3-ブタジエンと、1,3-ブタジエンと共重合し得る一種以上のビニル系単量体とを乳化重合して製造することができる。
単量体全量の100質量%における1,3-ブタジエンの割合が前記下限値以上であれば、十分な耐衝撃性が得られやすい。
ここでビニル系単量体としては、例えばスチレン、α-メチルスチレン等の芳香族ビニル、メチルメタクリレート、エチルメタクリレート等のメタクリル酸アルキルエステル、エチルアクリレート、n-ブチルアクリレート等のアクリル酸アルキルエステル、アクリロニトリル、メタクリロニトリル等の不飽和ニトリル、メチルビニルエーテル、ブチルビニルエーテル等のビニルエーテル、塩化ビニル、臭化ビニル等のハロゲン化ビニル、塩化ビニリデン、臭化ビニリデン等のハロゲン化ビニリデン、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、エチレングリコールグリシジルエーテル等のグリシジル基を有するビニル系単量体等が挙げられる。さらに、ジビニルベンゼン、ジビニルトルエン等の芳香族多官能ビニル化合物、エチレングリコールジメタクリレート、1,3-ブタンジオールジアクリレート等の多価アルコール、トリメタクリル酸エステル、トリアクリル酸エステル、アクリル酸アリル、メタクリル酸アリル等のカルボン酸アリルエステル、ジアリルフタレート、ジアリルセバケート、トリアリルトリアジン等のジおよびトリアリル化合物等の架橋性単量体を併用することもできる。
前記ビニル系単量体および架橋性単量体は、一種または二種以上を使用することができる。また、ブタジエン系ゴム重合体の重合時には必要に応じて、t-ドデシルメルカプタン、n-オクチルメルカプタン、α-メチルスチレン等の連鎖移動剤を使用することができる。
以下、ゴム部がジエン系ゴム状重合体であるゴム含有グラフト重合体(A)のことを、ジエン系ゴム含有グラフト重合体と呼ぶ。
ポリオルガノシロキサン系ゴム状重合体(ポリオルガノシロキサン系ゴムラテックス)は、ポリオルガノシロキサンゴム(S-1)またはポリオルガノシロキサン複合ゴム(S-2)から選ばれる1種または2種である。
ポリオルガノシロキサンゴム(S-1)は、オルガノシロキサン、ポリオルガノシロキサン用グラフト交叉剤(以下、「シロキサン交叉剤」とも言う。)、必要に応じてポリオルガノシロキサン用架橋剤(以下、「シロキサン架橋剤」とも言う。)および末端封鎖基を有するシロキサンオリゴマー等から成るオルガノシロキサン混合物を乳化重合して得られる。
環状オルガノシロキサンとしては、3員環以上の環状オルガノシロキサンが好ましく、3~6員環のものがより好ましい。
シロキサン交叉剤を用いることによって、任意のビニル共重合体と重合可能な官能基を有するポリオルガノシロキサンを得ることができる。ポリオルガノシロキサンが任意のビニル単量体と重合可能な官能基を有することにより、ポリオルガノシロキサンと、ポリ(メタ)アクリル酸アルキルエステルやビニル単量体を化学的に結合させることができる。
式(I)中、R1は、メチル基、エチル基、プロピル基、またはフェニル基を示す。R2は、アルコキシ基における有機基を示し、例えば、メチル基、エチル基、プロピル基、またはフェニル基を挙げることができる。nは、0、1または2を示す。Rは、式(I-1)~(I-4)で表されるいずれかの基を示す。
CH2=C(R4)-C6H4- ・・・(I-2)
CH2=CH- ・・・(I-3)
HS-(CH2)p- ・・・(I-4)
これらの式中、R3およびR4は、それぞれ、水素またはメチル基を示し、pは1~6の整数を示す。
この基を有するシロキサンとしては、例えば、β-メタクリロイルオキシエチルジメトキシメチルシラン、γ-メタクリロイルオキシプロピルメトキシジメチルシラン、γ-メタクリロイルオキシプロピルジメトキシメチルシラン、γ-メタクリロイルオキシプロピルトリメトキシシラン、γ-メタクリロイルオキシプロピルエトキシジエチルシラン、γ-メタクリロイルオキシプロピルジエトキシメチルシラン、δ-メタクリロイルオキシブチルジエトキシメチルシランを挙げることができる。
この基を有するシロキサンとしては、例えば、ビニルフェニルエチルジメトキシシランを挙げることができる。
この基を有するシロキサンとして、γ-メルカプトプロピルジメトキメチルシラン、γ-メルカプトプロピルメトキシジメチルシラン、γ-メルカプトプロピルジエトキシメチルシラン、γ-メルカプトプロピルエトキシジメチルシラン、γ-メルカプトプロピルトリメトキシシランを挙げることができる。
末端封鎖基を有するシロキサンオリゴマーとしては、例えば、ヘキサメチルジシロキサン、1,3-ビス(3-グリシドキシプロピル)テトラメチルジシロキサン、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン、メトキシトリメチルシランを挙げることができる。
オルガノシロキサン混合物(100質量%)中のシロキサン交叉剤の含有率は、0.1~10質量%の範囲であることが好ましい。
オルガノシロキサン混合物(100質量%)中のシロキサン架橋剤の含有率は、0~30質量%の範囲であることが好ましい。
本発明において、ポリオルガノシロキサン系複合ゴム(C1-3S-2)は、ポリオルガノシロキサンゴム(S-1)および複合ゴム用ビニル重合体を含む。好ましくは、ポリオルガノシロキサン複合ゴム(S-2)は、ポリオルガノシロキサンゴム(S-1)とポリアルキル(メタ)アクリレートゴムを含む。
複合ゴム用ビニル単量体としては、成形体の耐衝撃性が優れることから、n-ブチルアクリレートが好ましい。
反応性が異なる基を有することにより、他の成分と共に重合される際に不飽和基を温存した状態で複合ゴム内に組み込まれ、グラフト共重合体の形成を可能とする。例えば、メタクリル酸アリル、シアヌル酸トリアリル、イソシアヌル酸トリアリルが挙げられ、これらを単独で使用または2種以上併用できる。
アクリル交叉剤は、架橋性単量体と同様に重合性不飽和結合を2つ以上有するため、架橋剤としての機能も有する。
架橋性単量体の使用量が15部以下であると前記上限値以下であれば、成形体の耐衝撃性に優れる傾向にある。
架橋性単量体アクリル交叉剤の使用量が15部以下であると前記上限値以下であれば、成形体の耐衝撃性に優れる傾向にある。
ポリオルガノシロキサンゴム(S-1)の含有率が前記下限値以上であれば、成形体の耐衝撃性に優れる傾向にある。ポリオルガノシロキサンゴム(S-1)の含有率が前記上限値以下であれば、成形体の耐熱性に優れる傾向にある。
以下、ゴム部がポリオルガノシロキサン系ゴム状重合体であるゴム含有グラフト重合体(A)のことを、Si系ゴム含有グラフト重合体と呼ぶ。
ゴム含有グラフト重合体(A)の製造に用いる乳化剤は、特に限定されないが、例えば、脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルリン酸エステル塩、およびジアルキルスルホコハク酸塩等のアニオン性界面活性剤;ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン酸脂肪エステル、およびグリセリン脂肪酸エステル等のノニオン性界面活性剤;並びにアルキルアミン塩等カチオン性界面活性剤を使用することができる。また、これらの乳化剤は単独でまたは併用して使用することができる。
本発明のゴム含有グラフト重合体含有樹脂組成物は、本発明のゴム含有グラフト重合体(A)および熱可塑性樹脂(B)を含む。
ポリエステル、芳香族ポリカーボネート、スチレン系樹脂、塩化ビニル樹脂、ポリエチレン等のオレフィン樹脂等を含め多くの熱可塑性樹脂は、メチルメタクリレートを主成分とする樹脂改質剤が多用されているため、本発明のメチルメタクリレート主成分のグラフト鎖を有するゴム含有グラフト重合体(A)が好適に使用できる。そのため熱可塑性樹脂として特に限定せず、例えばエンジニアリングプラスチック、スチレン系樹脂、ポリエステル、オレフィン系樹脂、熱可塑性エラストマー、生分解性ポリマー、ハロゲン系重合体、アクリル系樹脂等多種多用な樹脂に応用できる。
これらは、それぞれ単独で含有されてもよく、または2種以上が含有されてもよい。
多塩基酸としては、例えばテレフタル酸、ナフタルジカルボン酸、シクロヘキシルジカルボン酸またはそのエステル類等が挙げられ、多価アルコールとしては、エチレングリコール、プロピレングリコール、ブタンジオール、ペンタンジオール、ネオペンチルグリコール、ヘキサンジオール、オクタンジオール、デカンジオール、シクロヘキサンジメタノール、ハイドロキノン、ビスフェノールA、2,2-ビス(4-ヒドロキシエトキシフェニル)プロパン、1,4-ジメチロールテトラブロモベンゼン、TBA-EO等が挙げられる。
ポリエステル系樹脂は単独重合体、共重合体あるいはこれら2種以上のブレンド物であってもよい。また、イーストマンケミカル製の商品名「PETG」等も好適に用いられる。
共重合体の成分としては、塩化ビニル以外に、エチレン、酢酸ビニル、メチルメタクリレート、およびブチルアクリレートなどのモノビニル化合物が挙げられる。
共重合体中の100質量%において、これらのモノビニル化合物はその合計量で20質量%以下の割合で含有されてもよい。
上記単独重合体、および共重合体は、それぞれ単独で含有されてもよく、または2種以上が含有されてもよい。
また、フッ素化重合体、臭素化重合体、ヨウ素化重合体等も挙げられる。
上記のメチルメタクリレートと共重合可能なビニル単量体としては、メチルアクリレート、エチルアクリレート、i-プロピルアクリレート、n-ブチルアクリレート、2-エチルヘキシルアクリレート等のアルキルアクリレート、エチルメタクリレート、プロピルメタクリレート、n-ブチルメタクリレート等のアルキルメタクリレート、スチレン、α-メチルスチレン、ビニルトルエン等の芳香族ビニル化合物等を挙げることができる。
なお、「部」は「質量部」を意味し、「%」は「質量%」を意味する。
冷却管、温度計および撹拌装置を備えたセパラブルフラスコ内に表1に示す水、乳化剤からなる「成分1」を添加した。このセパラブルフラスコ内に窒素気流を通ずることによりフラスコ内雰囲気の窒素置換を行い、液温を80℃まで昇温した。液温が80℃になった時点で表1に示すシードモノマー「成分2」を混合し、5分撹拌した後、表1に示す重合開始剤「成分3」を添加し、重合を開始させた(重合発熱により最大値で10℃程度上昇することがある)。その後、液温が78℃を下回らないように固定したまま25分保持した。
また、不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトンは、下記一般式(3)で示される、商品名「プラクセルFM1」(ダイセル社製)を使用した。
CH2=CCH3COO(CH2)2OCO(CH2)5OH ・・・(3)
表1に示す各成分を変更した以外は製造例1と同様にしてゴム含有グラフト重合体(A-2)~(A-3)および(B-1)~(B-5)の粉体を得た。但し、A-2およびA-3は「成分5」を強制乳化させた後滴下した。ゴムラテックス並びにグラフトラテックスの重合率はいずれも95%以上であった。
(1)ジエン系ゴム状重合体のラテックス(R-1)の製造
第一単量体混合液として表3に示す「成分7」を容量70Lのオートクレーブ内に仕込み、昇温して、液温が43℃になった時点で、表3に示す「成分8」のレドックス系開始剤を添加して反応を開始し、その後さらに液温を65℃まで昇温した。重合開始から3時間後に表3に示す「成分9」の重合開始剤を添加し、その1時間後から表3に示す「成分10」の第二単量体混合液、表3に示す「成分11」の乳化剤水溶液、表3に示す「成分12」の重合開始剤を8時間かけてオートクレーブ内に連続的に滴下した。重合開始から4時間反応させて、ゴム状重合体のラテックス(R-1)を得た。
ラテックス(R-1)222部(仕込みモノマー成分として80部)および脱イオン水143部を、攪拌機および還流冷却管を備えた反応容器内に仕込んだ。このセパラブルフラスコ内に窒素気流を通ずることによりフラスコ内雰囲気の窒素置換を行い、液温を70℃まで昇温した。次いで、表4に示す「成分13」からなる水溶液を加え、引き続き、30分間加熱攪拌を続けた。さらに、表4に示す「成分14」の混合物を強制乳化し、60分間かけて反応容器内に滴下し、引き続き、120分間加熱撹拌を続けた。このようにして、ゴム状重合体に対してビニル単量体をグラフト重合させて、ゴム含有グラフト重合体のラテックスを得た。重合率は100%であった。なお、アルキルジフェニルエーテルジスルホン酸ナトリウムは、ドデシルベンゼンスルホン酸ナトリウムは商品名「ネオペレックス G-15、KAO社製(ドデシルベンゼンスルホン酸ナトリウム16%水溶液)」を使用した。
また、不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトンは、前記一般式(3)で示され、商品名「プラクセルFM1」(ダイセル社製)を使用した。
表4に示す各成分を変更し、表4に示す「成分14」を強制乳化しなかった以外は製造例7と同様にしてゴム含有グラフト重合体(B-6、7)の粉体を得た。重合率は100%であった。このラテックス中の重合体粒子の体積平均粒子径は170nmであり、体積平均粒子径(Dv)を個数平均粒子径(Dn)で割った値は(Dv/Dn)=1.05であった。
1)ポリオルガノシロキサンゴムのラテックス(S-1)の製造
環状オルガノシロキサン混合物(信越シリコーン(株)製、製品名:DMC)を97.5部、テトラエトキシシラン(TEOS)を2部およびγ-メタクリロイロキシプロピルジメトキシメチルシラン(DSMA)を0.5部、混合してオルガノシロキサン混合物100部を得た。ドデシルベンゼンスルホン酸ナトリウム(DBSNa)を0.68部、ドデシルベンゼンスルホン酸(DBSH)を0.68部、脱イオン水200部中に溶解した水溶液を、前記混合物中に添加し、ホモミキサーにて10,000rpmで2分間撹拌した後、ホモジナイザーに20MPaの圧力で2回通し、安定な予備混合エマルションを得た。
次いで、冷却コンデンサーを備えた容量5リットルのセパラブルフラスコ内に前記エマルションを仕込んだ。該エマルションを85℃に加熱し、6時間維持して重合反応させた後、25℃に冷却し、25℃で12時間保持した。その後、5%水酸化ナトリウム水溶液を添加して反応液をpH7.0に中和して、ポリオルガノシロキサンゴムのラテックス(S-1)を得た。
このラテックスの固形分は40%であった。また、このラテックスの数平均粒子径(Dn)は170nm、体積平均粒子径(Dv)は210nmであり、Dv/Dnは1.24であった。
ポリオルガノシロキサンゴムのラテックス(S-1)を14.5部(仕込みモノマー成分として5部)容量5リットルのセパラブルフラスコ内に採取した。次いでこのセパラブルフラスコ内に、脱イオン水133部、ドデシルベンゼンスルホン酸ナトリウム3.3部(商品名「ネオペレックス G-15、KAO社製」)を添加混合した。次いでこのセパラブルフラスコ内に、アクリル酸n-ブチル(n-BA)55.4部、メタクリル酸アリル(AMA)0.6部、tert-ブチルハイドロパーオキサイド(t-BH)0.2部の混合物を添加した。
製造例12と同様にして作製したポリオルガノシロキサンとn-BAとの複合ゴムのラテックス(S-3)の温度を65℃に維持した状態で、n-BAを27.7部、AMAを0.3部、t-BHを0.1部の混合液を45分にわたって、このラテックス中に滴下した後、1時間加熱撹拌した。次いで、メタクリル酸メチル(MMA)を10.5部、n-BAを0.5部、t-BHを0.06部の混合液を20分にわたって、このラテックス中に滴下し重合した。滴下終了後、液温を65℃で1時間維持した後、25℃に冷却して、ゴム含有グラフト重合体(B-8)のラテックスを得た。
[1]乾燥試料の調製
以下(1)~(9)の操作を行ない、有機溶剤可溶分と有機溶剤不溶分を分離する。ここで、有機溶剤として、ジエン系ゴム含有グラフト重合体(A-4、B-6およびB-7)の場合はテトラヒドロフランを、アクリル系ゴム含有重合体およびSi系ゴム含有重合体(A-1~A-3、B-1~B-5、A-5およびB-8)の場合はアセトンを使用した。
(1)ゴム含有グラフト重合体1質量%、有機溶剤99質量%からなる溶液を調製する。
(2)(1)で調整した溶液を、1時間撹拌する。
(3)(2)で撹拌した溶液を、14,000rpm、60分間、遠心分離操作する。
(4)上澄みを抽出し、フラスコ内に入れる。
(5)沈殿物(有機溶剤不溶分)に再度有機溶剤を(1)と同量添加する。
(6)(3)~(5)の操作を3回繰り返す。
(7)フラスコを温度70℃の恒温槽中にセットして、エバポレータによって揮発分を留去する。
(8)フラスコ内の残存物を蒸気乾燥機にて80℃で8時間乾燥し、さらに真空乾燥機を用いて、65℃で6時間乾燥し、有機溶剤可溶分の乾燥試料を得る。
(9)沈殿物が入った容器を60℃の恒温槽中にセットして、有機溶剤を揮発させた後、真空乾燥機にて65℃で6時間乾燥し、有機溶剤不溶分の乾燥試料を得る。
上記操作(9)で得た有機溶剤不溶分の乾燥試料の質量から有機溶剤不溶分率を算出する。ゴム含有グラフト重合体の仕込み質量から有機溶剤不溶分質量を減じた値が有機溶剤可溶分となる。
ゴム含有グラフト重合体(A)からグラフト鎖を抽出し、組成分析を行った。グラフト鎖の抽出は、ジエン系ゴム含有グラフト重合体(A-4、B-6およびB-7)の場合はオゾン付加反応により行い、アクリル系ゴム含有重合体およびSi系ゴム含有重合体(A-1~A-3、B-1~B-5、A-5およびB-8)の場合は凍結粉砕により行った。
(凍結粉砕:A-1~A-2、B-1~B-5、A-5およびB-8)
粉砕容器として6751バイアル(ポリカーボネート管、スチールエンドプラグとスチロール型インパクター)を用い、ゴム含有グラフト重合体のアセトン不溶分0.9gを凍結粉砕(SPEX CertiPrep Ltd社製、製品名:SPEX6750 FREEZER/MILL :条件 予備冷却15分、粉砕2分間(20回/秒)、冷却時間2分冷却、4サイクル)し、凍結粉砕されたアセトン不溶分100mgを精秤し、50mLバイアルに移し、さらに30mLのアセトンを加えて攪拌後、10時間静置し、遠心分離機(日立高速冷却遠心機(CR22N)、日立工機(株)製)を用いて、温度:4℃、回転数:12,000rpmで60分間遠心分離を行い、可溶分と不溶分を分離する。得られた不溶分に再度アセトン30mLを添加し分散させ、遠心分離機にて遠心分離し、可溶分と不溶分に分離する。可溶分をイナートオーブンで窒素下、40度で10時間以上乾燥させ、「グラフト鎖乾燥試料」を得る。
下記(1)~(9)の操作に従い行った。
(1)ジエン系ゴム含有グラフト重合体のテトラヒドロフラン(THF)不溶分を6質量%、クロロホルムと塩化メチレンとの1:1混合液94質量%を調製し分散溶液とする。
(2)前記溶液をオゾン吸収ビンに入れ、-60℃以下に調製したドライアイス-メタノール溶液に漬ける。
(3)オゾン発生装置より発生したオゾンガスを吸収ビンに吹き込みオゾン付加を行う。
(4)オゾン付加後(吸収液が青色になる)、エアーを吹き込み過剰なオゾンを取り除く。
(5)ビーカーに還元剤(水素化ほう素ナトリウム)を10質量%、メタノール90質量%溶液に調整し、マグネチックスターラーで撹拌する。溶解後、(4)吸収液を入れ3時間以上撹拌する。
(6)撹拌後、(5)の溶液に、(5)溶液の質量の1/5に相当する質量の塩酸水溶液(1:1=塩酸:水)を加えて、3時間以上撹拌する。
(7)撹拌後、分液ロートに移し2層分離させる。この下層をナスフラスコに抜液する。
(8)ナスフラスコを65℃の恒温槽中にセットして、エバポレータによって揮発分を留去する。
(9)ナスフラスコ内の残存物を65℃で8時間以上、真空乾燥して「グラフト鎖乾燥試料」を得る。
下記(1)および(2)の操作に従い分析した。
(1)前記[1]の操作で得た「グラフト鎖乾燥試料」を、熱分解GC-MS(ガスクロマトグラフィー質量分析計)を用い、下記1)~4)に示す条件で、500℃で熱分解させ、グラフト鎖のポリマー組成比を測定した。
1)強極性カラムで極性物質を分析、カラムの商品名「DP-FFAR、アジレント・テクノロジー株式会社製、30m×0.25mm×0.25μm」
2)カラム流量:1.0mL/min
3)注入口、インターフェース温度:230℃
4)熱分解温度:500℃
ナノ粒子径分布測定装置 SALD-7100(島津製作所(株)製)を使用し測定した。
以下の手順により、グラフトラテックスの重合率を測定する。
(i)アルミニウム皿の質量(x)を0.1mgの単位まで測定する。
(ii)アルミニウム皿に重合体(X)のラテックスを約1g取り、重合体(X)のラテックスの入ったアルミニウム皿の質量(y)を0.1mgの単位まで測定する。
(iii)重合体(X)のラテックスの入ったアルミニウム皿を180℃の乾燥機に入れ、45分間加熱する。
(iv)アルミニウム皿を乾燥機から取出し、デシケーター内で25℃まで冷却し、その質量(z)を0.1mgの単位まで測定する。
(v)以下の式に基づいて、重合体(X)のラテックスの固形分濃度(%)を算出する。
固形分濃度(%)={(z-x)/(y-x)}×100
(vi)重合体(X)を製造する際に仕込む全単量体が重合した際の固形分濃度に対する(v)により算出した固形分濃度の百分率(%)を、グラフトラテックス製造終了時の重合率とする。
製造例1で得られたゴム含有グラフト重合体(A-1)とポリブチレンテレフタレート樹脂(「ノバデュラン5010R5」(商品名)を表5に示す組成で配合し、混合し、混合物を得た。この混合物を、バレル温度260℃に加熱した脱揮式二軸押出機(池貝鉄工社製、PCM-30)に供給して混練し、ゴム含有グラフト重合体(A-1)が15質量%配合された実施例1の樹脂組成物のペレットを作製した。
各ペレットを別個に、住友射出成形機SE100DU(住友重機械工業(株)製)に供給し、シリンダー温度260℃、金型温度60℃にて、長さ80mm×幅10mm×厚さ4mmの成形体(試験片)を得た。
シャルピー衝撃試験はISO-179-1に準拠し、ISO2818に準拠したTYPEAのノッチを刻んで測定した。
各ペレットを別個に、住友射出成形機SE100DU(住友重機械工業(株)製)に供給し、シリンダー温度260℃、金型温度60℃、1点ゲート方式にて、JIS-7139で定める多目的試験片(A1)形状を得た。
引張試験はISO-527に準拠し、引張速度は20mm/minとした。
各ペレットを、それぞれ別個に、住友射出成形機SE100DU(住友重機械工業(株)製)に供給し、シリンダー温度260℃、金型温度60℃にて、JIS-7139で定める多目的試験片(A1)形状を得た。
この際、以下の手順に従って該当する試験片を得た。
(1)2点ゲートにて射出成形時の射出圧および保持圧を調整し、試験片中央にウェルドラインが来るように作製(図1a)
(2)(1)のときの保持圧を4MPa上げることで図1bの試験片を作製
引張試験はISO-527に準拠し、引張速度は20mm/minとした。
本発明の評価におけるウェルド強度は、図1bに示す試験片の引張試験の破断伸度と定義する。
各ペレットを、それぞれ別個に、住友射出成形機SE100DU(住友重機械工業(株)製)に供給し、シリンダー温度260℃、金型温度60℃にて、長さ100mm×幅50mm×厚さ2mmの成形体(試験片)を得た。試験片から、図2に示すよう、長さ10mm×幅5mm×厚さ2mmの試片を切り出した。切り出した試片を、図2にて観察面と記載した断面において、中央付近が薄切面となるよう、ウルトラミクロトーム(製品名:Leica EM UC7、ライカ マイクロシステムズ(株)製)により面出しおよびトリミングした。得られた試片を2.0質量%四酸化オスミウム水溶液(和光純薬(株)製)に浸漬させ、25℃で12時間染色したのち、上記ウルトラミクロトームにより、薄片厚さ50nm、切削速度0.4mm/secの条件で薄片を切り出し、支持膜付き銅グリッドの上に回収した。グリッド上に回収した薄片を0.5質量%四酸化ルテニウム水溶液(日新EM(株)製)蒸気により、25℃で10分染色したのち、透過型電子顕微鏡(製品名:H-7600、日立(株)製)により、加速電圧80kV条件で観察した。
Ac-CL:不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトン(登録商標)「プラクセルFM-1」(ダイセル社製)
CL:カプロラクトン単位
MMA:メチルメタクリレート
GMA:グリシジルメタクリレート
PC:芳香族ポリカーボネート樹脂((登録商標)「ユーピロンS-2000F」)
Ac-CL:不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトン(登録商標)「プラクセルFM-1」(ダイセル社製)
CL:カプロラクトン単位
MMA:メチルメタクリレート
GMA:グリシジルメタクリレート
HEMA:2-ヒドロキシエチルメタクリレート
PC:芳香族ポリカーボネート樹脂((登録商標)「ユーピロンS-2000F」)
Ac-CL:不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトン(登録商標)「プラクセルFM-1」(ダイセル社製)
CL:カプロラクトン単位
MMA:メチルメタクリレート
St-AN:スチレンとアクリロニトリルの共重合体
Claims (23)
- グラフト鎖を有するゴム含有グラフト重合体であって、
前記ゴム含有グラフト重合体を有機溶剤と混合して、有機溶剤不溶分と有機溶剤可溶分に分離させたとき、前記有機溶剤不溶分に含まれるグラフト鎖中にカプロラクトン単位を含むゴム含有グラフト重合体。 - 前記有機溶剤不溶分のグラフト鎖中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.1~40質量部含む、請求項1に記載のゴム含有グラフト重合体。
- 前記有機溶剤不溶分のグラフト鎖中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.5~30質量部含む、請求項2に記載のゴム含有グラフト重合体。
- 前記有機溶剤不溶分のグラフト鎖中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を1.5~20質量部含む、請求項3に記載のゴム含有グラフト重合体。
- 前記有機溶剤不溶分に凍結粉砕を施し、凍結粉砕された有機溶剤不溶分を有機溶剤と混合して、凍結粉砕後の有機溶剤不溶分と凍結粉砕後の有機溶剤抽出物に分離させたとき、前記凍結粉砕後の有機溶剤抽出物にカプロラクトン単位を含む、請求項1に記載のゴム含有グラフト重合体。
- 前記凍結粉砕後の有機溶剤抽出物に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.1~40質量部含む、請求項5に記載のゴム含有グラフト重合体。
- 前記凍結粉砕後の有機溶剤抽出物に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.5~30質量部含む、請求項6に記載のゴム含有グラフト重合体。
- 前記凍結粉砕後の有機溶剤抽出物に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を1.5~20質量部含む、請求項7に記載のゴム含有グラフト重合体。
- 前記有機溶剤不溶分にオゾン付加反応を施し、オゾン付加された有機溶剤不溶分を有機溶剤と混合して、オゾン付加反応後の有機溶剤不溶分とオゾン付加反応後の有機溶剤抽出物に分離させたとき、前記オゾン付加反応後の有機溶剤抽出物に、カプロラクトン単位を含む、請求項1に記載のゴム含有グラフト重合体。
- 前記オゾン付加反応後の有機溶剤抽出物中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.1~40質量部含む、請求項9に記載のゴム含有グラフト重合体。
- 前記オゾン付加反応後の有機溶剤抽出物中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を0.5~30質量部含む、請求項10に記載のゴム含有グラフト重合体。
- 前記オゾン付加反応後の有機溶剤抽出物中に含まれる、ガラス転移温度(Tg)が60℃以上の成分100質量部に対して、カプロラクトン単位を1.5~20質量部含む、請求項11に記載のゴム含有グラフト重合体。
- ゴムラテックス50~95質量%に、下記一般式(1)で表されるビニル単量体(f-1)を含むグラフト用単量体(b)5~50質量%を乳化グラフト重合させて得られるグラフト重合体。
CH2=CR1COO(CH2)qO[CO(CH2)mO]nH ・・・(1)
(式中、R1は水素またはメチル基を表し、qは2~5、mは3~10、nは1~10の整数を表す)。 - 前記ビニル単量体(f-1)が、下記一般式(2)で表されるビニル単量体(f-2)である請求項13に記載のゴム含有グラフト重合体。
CH2=CR2COO(CH2)qO[CO(CH2)5O]nH ・・・(2)
(式中、R2は水素またはメチル基を表し、qは2~5、nは1~5の整数を表す)。 - グラフト用単量体(b)がメチルメタクリレートを含む、請求項13または14に記載のゴム含有グラフト重合体。
- 前記ゴム含有グラフト重合体(100質量%)中、前記ビニル単量体(f-1)を0.5~50質量%含む、請求項13~15のいずれか一項に記載のゴム含有グラフト重合体。
- グラフトさせるゴムの粒子径が50~400nmである、請求項1~16のいずれか一項に記載のゴム含有グラフト重合体。
- 請求項1~17のいずれか一項に記載のゴム含有グラフト重合体および熱可塑性樹脂(B)を含む、ゴム含有グラフト重合体含有樹脂組成物。
- 前記熱可塑性樹脂(B)がポリエステル樹脂である、請求項18に記載のゴム含有グラフト重合体含有樹脂組成物。
- 前記熱可塑性樹脂(B)が芳香族ポリカーボネート樹脂とポリエステル樹脂のアロイである、請求項18に記載のゴム含有グラフト重合体含有樹脂組成物。
- 前記熱可塑性樹脂(B)が芳香族ポリカーボネート樹脂とスチレン系樹脂のアロイである、請求項18に記載のゴム含有グラフト重合体含有樹脂組成物。
- 請求項18~21のいずれか一項に記載のゴム含有グラフト重合体含有樹脂組成物を成形してなる成形体。
- 射出成形体である、請求項22に記載の成形体。
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EP18896964.6A EP3733727A4 (en) | 2017-12-25 | 2018-12-19 | GRAFT POLYMER INCLUDING A RUBBER, AND A RESIN COMPOSITION INCLUDING A GRAFT POLYMER WITH RUBBER CONTENT AND A MOLDED BODY OF THE SAME |
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