JP5896716B2 - Resin composition and heat insulating member comprising the resin composition - Google Patents

Description

  The present invention relates to a resin composition and a heat insulating member made of the resin composition.

  Conventionally, a method for producing a foamed molded article containing bubbles by chemical foaming using a gas accompanying a chemical reaction of a foaming agent or physical foaming such as supercritical foaming by injecting a high pressure gas and releasing the pressure. It has been known. Such a foam-molded product is suitably used as a heat insulating member, for example. However, when this foamed molded product is used as a base material for vacuum molding or a film for film insert molding, there is a problem that bubbles are crushed, and the molding method is limited.

  On the other hand, hollow particles, such as hollow glass spheres, are used as additives and fillers for polymer compounds (Patent Document 1), and the method for producing a molded body containing hollow glass spheres is the above foam molding. Compared to the body manufacturing method, it has a feature that it is easy to produce closed-cell foam. However, when trying to produce a molded body containing hollow glass spheres, the hollow glass spheres tend to be destroyed during kneading or molding, and the main uses of polymer materials containing hollow glass spheres are paints, coatings Agents, plastisols and the like.

Japanese Patent Laid-Open No. 02-069336 Japanese Patent Laid-Open No. 06-93060 Japanese National Patent Publication No. 05-507737 JP-A-11-335432

Macromol. Chem. Phys. 2000, 201, p. 1108 to 1114

  Accordingly, an object of the present invention is to provide a resin composition that is less likely to break hollow particles at the time of kneading or molding, has excellent heat insulating properties (typically temperature sensitivity), and light weight, and a heat insulating member comprising the resin composition. Is to provide.

According to the present invention, the above object is [1] a resin composition containing 20 to 95% by mass of a (meth) acrylic block copolymer and 5 to 80% by mass of hollow particles;
[2] The (meth) acrylic block copolymer has at least one polymer block (A) mainly composed of (meth) acrylic acid ester having a glass transition temperature (Tg) of 25 ° C. or higher, and 25 ° C. The total mass of the polymer block (A) in the (meth) acrylic block copolymer having at least one polymer block (B) mainly composed of (meth) acrylic acid ester having a Tg of less than 5 to 45% by mass, and the total mass of the polymer block (B) is 55 to 95% by mass;
[3] The resin composition according to [2], wherein the (meth) acrylic block copolymer has a portion in which the polymer block (A), the polymer block (B), and the polymer block (A) are bonded in this order. object;
[4] A heat insulating member obtained by molding the resin composition according to any one of [1] to [3];
[5] A heat-insulating sealant member obtained from the resin composition according to any one of [1] to [3]; and
[6] An adhesive heat insulating member obtained from the resin composition according to any one of [1] to [3].

  According to the present invention, a resin composition excellent in heat insulating properties (typically temperature sensitivity) and light weight, and a heat insulating member made of the resin composition can be obtained when the hollow particles are less crushed during kneading or molding.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention contains 20 to 95% by mass of a (meth) acrylic block copolymer and 5 to 80% by mass of hollow particles. In this specification, (meth) acrylic is a generic term for acrylic and methacrylic.

  The (meth) acrylic block copolymer used in the present invention means a block copolymer having two or more (meth) acrylic acid ester polymer blocks. The (meth) acrylic acid ester polymer block is made of a polymer mainly composed of (meth) acrylic acid ester. Here, having a (meth) acrylic acid ester as a main component means that there are the most (meth) acrylic acid ester units having no reactive group among the monomer units contained in the polymer block, The (meth) acrylic acid ester unit having no reactive group in the (meth) acrylic acid ester polymer block is usually 50% by mass to 100% by mass, preferably 80% by mass to 100% by mass, and more preferably 90% by mass. % To 100% by mass, and the (meth) acrylic acid ester unit having no reactive group may be 100% by mass.

  Examples of the (meth) acrylic acid ester having no reactive group constituting the (meth) acrylic acid ester polymer block include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid n. -Propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate (Meth) acrylates such as isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, pentadecyl (meth) acrylate, dodecyl (meth) acrylate; ) (Meth) acrylic acid such as cyclohexyl acrylate, isobornyl (meth) acrylate Alkyl; aryl (meth) acrylates such as phenyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate A phenoxyalkyl (meth) acrylate such as phenoxyethyl (meth) acrylate; These (meth) acrylic acid esters may be used alone or in a combination of two or more.

  Functionality such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, etc., as long as the properties of the (meth) acrylic block copolymer used in the present invention are not impaired. A (meth) acrylic acid ester having a group may be used. These are used in an amount of usually 40% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, based on the total mass of monomers used for the synthesis of each polymer block.

  Moreover, as long as it does not impair the characteristic of the (meth) acrylic block copolymer used for this invention, as a monomer used for the synthesis | combination of the said (meth) acrylic acid ester polymer block, another single quantity as needed The body may be used in combination.

  Examples of these other monomers include methacrylic acid, acrylic acid, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, isobutene, butadiene, isoprene, Examples include octene, vinyl acetate, maleic anhydride, vinyl chloride, and vinylidene chloride. These other monomers are usually 40% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less based on the total mass of the monomers used for the synthesis of each polymer block. Used.

The (meth) acrylic block copolymer used in the present invention may have other polymer blocks as required in addition to the (meth) acrylic acid ester polymer block.
Examples of other polymer blocks include methacrylic acid, acrylic acid, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, isobutene, butadiene, isoprene, octene. Polymer block or copolymer block synthesized from monomers such as vinyl acetate, maleic anhydride, vinyl chloride, vinylidene chloride, polymer comprising polyethylene terephthalate, polybutylene terephthalate, polylactic acid, polyurethane, polydimethylsiloxane Examples include blocks. The polymer block also includes a hydrogenated polymer block synthesized from a monomer containing a diene monomer such as butadiene or isoprene.

  The molecular weight of the (meth) acrylic block copolymer is a viewpoint of improving workability when the resin composition of the present invention is produced by kneading, and melt moldability when the heat insulating member of the present invention is produced by thermoforming. From the viewpoint of improving the viscosity, the weight average molecular weight (Mw) in terms of standard polystyrene determined by gel permeation chromatography measurement is preferably 10,000 to 150,000, more preferably 30,000 to 100,000. is there.

  The molecular weight distribution [weight average molecular weight / number average molecular weight (Mw / Mn)] of the (meth) acrylic block copolymer is the viewpoint of moldability when producing the heat insulating member of the present invention, and the smoothness of the surface of the heat insulating member. Therefore, it is preferably in the range of 1.01-2.20, more preferably in the range of 1.05-1.60. If the molecular weight distribution is larger than 2.20, the molding processability may be impaired due to an increase in the high molecular weight, and the disadvantage of poor surface smoothness due to bleeding may occur due to an increase in low molecular weight components.

  The (meth) acrylic block copolymer has a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride group, an amino group, or a trimethoxysilyl group in the molecular chain or at the molecular chain end as necessary. Also good.

  The melt flow rate (MFR) of the (meth) acrylic block copolymer improves the workability when the resin composition containing the (meth) acrylic block copolymer of the present invention is prepared by melt kneading. From the viewpoint and the viewpoint of improving the melt moldability when the heat insulating member of the present invention is produced by thermoforming, preferably 40 g / 10 min (230 ° C., 2.16 kgf) or more, more preferably 80 g / 10 min. It is (230 degreeC, 2.16kgf) or more.

  As the (meth) acrylic block copolymer, at least one polymer block (A) mainly composed of (meth) acrylic acid ester having a glass transition temperature (Tg) of 25 ° C. or higher and a Tg of less than 25 ° C. A (meth) acrylic block copolymer having at least one polymer block (B) mainly composed of a (meth) acrylic acid ester having a salt is preferred.

  Tg of the polymer block (A) is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 100 ° C. or higher. When an acrylic block copolymer having a polymer block (A) having a Tg of 25 ° C. or higher is used, a resin composition having excellent heat resistance can be obtained.

  Examples of the (meth) acrylic acid ester constituting the polymer block (A) include, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate. , Methacrylates such as isobornyl methacrylate, 2-methoxyethyl methacrylate and phenyl methacrylate; acrylic acid such as methyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, cyclohexyl acrylate, and phenyl acrylate Examples include esters.

  Among these, from the viewpoint of improving the heat insulation performance (typically temperature sensitivity) and heat resistance of the obtained resin composition and heat insulation member, methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, amyl methacrylate Cyclohexyl methacrylate, isobornyl methacrylate, phenyl methacrylate, methyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, and phenyl acrylate are preferred, and methyl methacrylate is more preferred. These (meth) acrylic acid esters may be used alone or in a combination of two or more. Moreover, when the said (meth) acrylic-type block copolymer contains two or more polymer blocks (A), these polymer blocks (A) may be the same or different.

  The weight average molecular weight (Mw) of the polymer block (A) is used to improve the workability when the resin composition of the present invention is produced by melt kneading, and when the heat insulating member of the present invention is produced by thermoforming. From the viewpoint of improving the melt moldability, the range is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

  The Tg of the polymer block (B) is preferably 0 ° C. or lower, more preferably −15 ° C. or lower. By using a (meth) acrylic block copolymer in which the Tg of the polymer block (B) is less than 25 ° C., the polymer block (B) is more adhesive when it is more excellent in flexibility and impact resistance and needs to be tacky. A resin composition having excellent properties can be obtained.

  Examples of the (meth) acrylic acid ester constituting the polymer block (B) include n-propyl methacrylate, n-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-methacrylic acid 2- Methacrylic acid esters such as ethylhexyl, pentadecyl methacrylate, dodecyl methacrylate, phenoxyethyl methacrylate; ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, Amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-acrylic acid 2- Acrylic acid esters such as Tokishiechiru the like.

  Among these, from the viewpoint of improving adhesiveness when the obtained resin composition and the heat insulating performance (typically temperature sensitivity), flexibility, impact resistance, and adhesiveness of the heat insulating member are required. , N-propyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, phenoxyethyl methacrylate, methyl acrylate, ethyl acrylate, n-acrylate Propyl, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, benzyl acrylate, Phenoxyethyl acrylate, acrylic 2-methoxyethyl acid is preferred, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, benzyl acrylate, acrylic acid Phenoxyethyl and 2-methoxyethyl acrylate are more preferable. These (meth) acrylic acid esters may be used alone or in a combination of two or more. Moreover, when two or more polymer blocks (B) are contained in the acrylic block copolymer, these polymer blocks (B) may be the same or different.

  In addition, as long as the polymer block (A) satisfies the above Tg requirements, the polymer block (B) may contain (meth) acrylic acid ester constituting the polymer block (B) as a structural unit. As long as the above Tg requirements are satisfied, a (meth) acrylic acid ester constituting the polymer block (A) may be included as a structural unit.

The glass transition temperature of the polymer block (A) and the polymer block (B) in the (meth) acrylic block copolymer is observed in the curve obtained by DSC measurement of the (meth) acrylic block copolymer. Is an extrapolation start temperature (Tgi) of the transition region of the polymer block (A) and the polymer block (B). Specific measurement methods will be described in detail in Examples. Based on the curve obtained by DSC measurement, in the (meth) acrylic block copolymer used in the present invention, a plurality of glass transition temperatures derived from the polymer block (A) and the polymer block (B) are required. The glass transition temperature derived from the polymer block (A) and the polymer block (B) is the glass transition temperature of the polymer having the same chemical structure (monomer composition, stereoregularity, etc.) as the respective polymer blocks. Therefore, it can be easily determined which polymer block the plurality of glass transition temperatures are derived from. The polymer having the same chemical structure as the polymer block (A) and the polymer block (B) is obtained by analyzing the (meth) acrylic block copolymer by ¹ H-NMR, ¹³ C-NMR or the like. The chemical structure such as the monomer composition and stereoregularity of the polymer block (A) and the polymer block (B) can be obtained, and the polymerization can be appropriately performed so that the chemical structure is reproduced.

  The resin composition containing the (meth) acrylic block copolymer of the present invention has a reduced elastic deformation at the time of kneading or molding, and can retain its form when used as a heat insulating member. It is desirable to have flexibility. Therefore, in the case of a (meth) acrylic block copolymer having a polymer block (A) and a polymer block (B), the total of the polymer block (A) in the (meth) acrylic block copolymer The mass is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 25% by mass, and the total mass of the polymer block (B) is preferably 55 to 95% by mass, more preferably. Is 60 to 90 mass%, more preferably 75 to 85 mass%. When the proportion of the polymer block (A) is smaller than 5% by mass, the adhesiveness becomes too high when the (meth) acrylic block copolymer and the hollow particles are kneaded, making it difficult to handle the raw material. In addition, the molecular weight of the polymer block (A) becomes too small, and the heat resistance and shape retention of the heat insulating member may be inferior. When the ratio of the polymer block (A) is larger than 45% by mass, the flexibility and impact resistance of the heat insulating member tend not to be sufficiently exhibited. Moreover, when using the heat insulation member of this invention as an adhesive heat insulation member, the total mass of the polymer block (A) in a (meth) acrylic-type block copolymer from a viewpoint of a handleability and adhesiveness balance. Is preferably 5 to 25% by mass, and the total mass of the polymer block (B) is preferably 75 to 95% by mass.

  Examples of the bonding form of the (meth) acrylic block copolymer having the polymer blocks (A) and (B) include, for example, linear, branched, radial, or a combination of two or more of them. However, it is preferably a straight chain. Specific examples of the acrylic block copolymer include a diblock copolymer in which two constituting polymer blocks are linearly bonded, and a triblock copolymer in which three polymer blocks are linearly bonded. , A tetrablock copolymer in which four polymer blocks are linearly bonded, and a pentablock copolymer in which five polymer blocks are linearly bonded. Among these, the polymer block (A), the polymer block (B), and the polymer block (A) are combined in this order from the viewpoint of the balance of moldability (melt flowability), mechanical properties, and adhesiveness. A (meth) acrylic block copolymer having a moiety is preferred. Examples of such a (meth) acrylic block copolymer include a triblock copolymer comprising a polymer block (A) -polymer block (B) -polymer block (A), and a polymer block (A)- The tetrablock copolymer etc. which consist of a polymer block (B) -polymer block (A) -polymer block (B) are mentioned.

Moreover, from the viewpoint of producing an adhesive heat insulating member, a triblock copolymer and a mixture of a triblock copolymer and a diblock copolymer are preferable.
The (meth) acrylic block copolymer preferably has a stable processability. For that purpose, it is preferable that the molecular weight distribution of the (meth) acrylic block copolymer is not too large, specifically Is preferably in the range of 1.01-2.20, more preferably in the range of 1.05-1.60. As a method for producing such a (meth) acrylic block copolymer, a living polymerization method capable of highly controlling the molecular structure is preferable.

  Living polymerization is a method of polymerizing the monomers of the polymer block constituting the block copolymer and synthesizing the block copolymer by polymerizing other monomers before the polymerization is deactivated or stopped. For example, a method of polymerizing using an organic rare earth metal complex as a polymerization initiator (see Patent Document 2), presence of a mineral salt such as an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator Under anionic polymerization (see Patent Document 3), anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound (see Patent Document 4), atom transfer radical polymerization method (ATRP) ) (See Non-Patent Document 1).

  Among the above production methods, the method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound has little deactivation during the polymerization, so that there is little mixing of the deactivating component homopolymer, There are few residual monomers in the (meth) acrylic block copolymer obtained because the polymerization conversion rate of a body is high. For this reason, it is excellent in control of molecular weight, molecular weight distribution, and structure, there is little content of block copolymers other than the target block structure, and it is excellent in the balance of melt-kneading property and mechanical physical property. And since living polymerization is possible on comparatively moderate temperature conditions, it is excellent in industrial productivity. From the above points, the (meth) acrylic block copolymer is preferably produced by a method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound.

Examples of the organoaluminum compound include compounds represented by the following general formula (I).
AlR ¹ R ² R ³ (I)
(In the above formula (I), R ¹ , R ² and R ³ are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. An aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a substituent Represents an optionally substituted N, N-disubstituted amino group or a halogen atom, wherein two selected from R ¹ , R ² and R ³ are bonded to each other and have a substituent; An alkylene group which may have a substituent, an arylene group which may have a substituent, an arylene alkyl group which may have a substituent, an alkylenedioxy group which may have a substituent, and a substituent An aryleneoxy group which may be present may be formed.)

  Examples of the organoaluminum compound represented by the above formula (I) include isobutyl bis (2,6-di-tert-butylphenoxy) aluminum, isobutyl bis ( 2,6-di-tert-butyl-4-methylphenoxy) aluminum and isobutyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum are preferred.

  As the organic alkali metal compound, an organic lithium compound is preferable, for example, alkyllithium or alkyldilithium such as n-propyllithium, n-butyllithium, sec-butyllithium and tetramethylenedilithium; aryl such as phenyllithium and xylyllithium. Examples include lithium or aryl dilithium; aralkyl lithium such as dilithium or aralkyl dilithium produced by the reaction of benzyl lithium, diisopropenylbenzene and butyl lithium; lithium amide such as lithium dimethylamide; lithium alkoxide such as methoxy lithium. Among these, alkyl lithium is preferable because of high polymerization initiation efficiency, t-butyl lithium and sec-butyl lithium are preferable, and sec-butyl lithium is more preferable.

  The anionic polymerization is usually performed in the presence of an inert solvent. Examples of the inert solvent include hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride; ethers such as tetrahydrofuran and diethyl ether.

Examples of the method for producing a (meth) acrylic block copolymer by the above-described anionic polymerization include a method of sequentially polymerizing each polymer block.
The resin composition of the present invention contains a (meth) acrylic block copolymer as an essential component, and the resin composition contains one or more (meth) acrylic block copolymers. Also good.

  The resin composition of the present invention is characterized by containing 5 to 80% by mass of hollow particles. Here, the hollow particles mean particles having voids inside the particles. The hollow particles may have a single void or a plurality of voids.

  The porosity of the hollow particles is not particularly limited as long as the resin composition can be used as a heat insulating member, but is usually 30 to 99% by volume, preferably 40 to 90% by volume, more preferably 50 to 80% by volume. . When the porosity is in the above range, the breakage of the hollow particles can be suppressed, and the effect of blending the hollow particles is sufficiently exhibited. The porosity is the ratio of the total volume of the void to the total volume of the hollow particles. From the measured value of the refractive index of the hollow particles, the theoretical value of the refractive index of the material forming the hollow particles and the void portion It can be calculated as the volume fraction of the refractive index (n≈1.00: assuming the refractive index of air).

  The average particle diameter of the hollow particles is usually 0.1 μm to 70 μm, preferably 1 μm to 50 μm, more preferably 5 μm to 40 μm. When the average particle diameter is in the above range, the processability is excellent and the effect of blending the hollow particles is sufficiently exhibited. The average particle diameter is a volume average particle diameter measured by a laser diffraction / scattering method.

The material forming the hollow particles may be an organic material or an inorganic material.
Examples of the organic material include synthetic resins such as acrylic resin, styrene resin, polyester, polyurethane, and epoxy resin.

  Examples of the inorganic material include metal oxides such as silica, alumina, titania and zirconia, metal halides such as magnesium fluoride, inorganic materials mainly composed of these, and natural minerals.

Among the above, hollow particles formed of an inorganic material are preferable from the viewpoint that deformation or the like of the hollow particles hardly occurs during melt kneading or molding.
Hollow particles formed from such inorganic materials are commercially available, for example, “Glass Bubbles” (manufactured by Sumitomo 3M Co., Ltd.), “Q-CEL”, Sphericel (manufactured by Potters Ballotini Co., Ltd.), Hollow particles formed from inorganic glass such as “Sirinax” (manufactured by Nippon Steel Mining Co., Ltd.) and artificial materials such as silica; Hollow particles formed from fly ash such as fly ash balloon (manufactured by Tokai Kogyo Co., Ltd.) And hollow particles formed from naturally-derived materials such as volcanic glassy deposits such as Shirasu Balloon (for example, manufactured by Shirazuu Co., Ltd.) and pearlite (for example, “Mitsui Perlite” manufactured by Mitsui Mining Co., Ltd.). Among these, hollow particles formed from an artificial material are preferable in terms of few impurities, and hollow particles formed from inorganic glass are particularly preferable.

  Content of the (meth) acrylic-type block copolymer in the resin composition of this invention is 20-95 mass%. From the viewpoint of moldability of the resin composition and heat insulating performance of the heat insulating member, the content is preferably 30 to 80% by mass, and more preferably 35 to 70% by mass.

  From the viewpoint of imparting adhesiveness to the heat insulating member, the content of the (meth) acrylic block copolymer in the resin composition is preferably 50 to 70% by mass. The heat insulating member made of the resin composition having such a composition is useful as an adhesive heat insulating member such as an adhesive sheet, a heat insulating sealing member, or the like. Moreover, when adhesiveness is not calculated | required in a heat insulation member, it is preferable that content of the (meth) acrylic-type block copolymer in a resin composition is 35-70 mass%. A heat insulating member made of the resin composition having such a composition is suitable as an ordinary molded product.

  Content of the hollow particle in the resin composition of this invention is 5-80 mass%. From the viewpoint of the moldability of the resin composition and the heat insulating performance of the heat insulating member, the content is preferably 20 to 70% by mass, and more preferably 30 to 65% by mass.

  From the viewpoint of imparting adhesiveness to the heat insulating member, the content of the hollow particles in the resin composition is preferably 30 to 50% by mass. Moreover, when adhesiveness is not calculated | required in a heat insulation member, it is preferable that content of the hollow particle in a resin composition is 30 mass%-65 mass%.

  The resin composition may contain other polymers such as resin and rubber as long as the effects of the present invention are not impaired. Resin compositions are softeners, lubricants, plasticizers, adhesives, tackifying resins, heat stabilizers, antioxidants, light stabilizers, antistatic agents, flame retardants, foaming agents, colorants, dyeing agents, You may contain additives, such as a filler. These other polymers and additives may be used alone or in combination of two or more.

  Examples of the other polymers include acrylic resins other than (meth) acrylic block copolymers, such as acrylic resins such as polymethyl methacrylate and methacrylate ester copolymers; polyethylene, ethylene-vinyl acetate copolymer. Olefin resins such as polymer, polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene; ethylene ionomer; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin Styrene resins such as AES resin, AAS resin, ACS resin, MBS resin; polyester resins such as methyl methacrylate-styrene copolymer; polyethylene terephthalate, polybutylene terephthalate, polylactic acid; nylon 6, nylon 66, polyamide elastomer Polyamide mers and the like; polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene - vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, polyurethanes, modified polyphenylene ether, polyphenylene sulfide, and the like silicone rubber-modified resins. Among these, acrylic resin, AS resin, polylactic acid, and polyvinylidene fluoride are preferable from the viewpoint of compatibility with the (meth) acrylic block copolymer contained in the resin composition.

Moreover, when the heat stabilizer or antioxidant is contained in the resin composition as an additive, heat resistance and weather resistance are improved.
Moreover, when tackifying resin is contained in a resin composition, adhesiveness will become favorable. Examples of the tackifying resin include rosin derivatives such as rosin ester, gum rosin, tall oil rosin, hydrogenated rosin ester, maleated rosin, and disproportionated rosin ester; terpene phenol resin, α-pinene, β-pinene, limonene, and the like. (Hydrogenated) petroleum resin, coumarone-indene resin, hydrogenated aromatic copolymer, styrene resin, phenol resin, xylene resin and the like.

These other polymers and additives may be added when the resin composition is molded to produce a heat insulating member.
When the resin composition of the present invention is used as a heat insulating member, an elastic modulus, flexibility, and impact resistance that can maintain the form are required. Moreover, adhesiveness is needed as needed.

  The elastic modulus of the resin composition of the present invention can be appropriately selected depending on the application. For example, when using a resin composition as a non-adhesive thing, it is preferable that the tensile elasticity modulus in 25 degreeC is 100 Mpa-2500 Mpa, and it is more preferable that it is 200 Mpa-2000 Mpa. If the tensile elastic modulus at 25 ° C. is greater than 2500 MPa, the flexibility is insufficient and the bending workability and the flexibility tend to be inferior. When the heat insulating member of the present invention is used as a member requiring adhesiveness such as a heat insulating sealing member or an adhesive heat insulating member, the tensile elastic modulus at 25 ° C. is preferably 100 MPa or less.

  The resin composition of this invention can be manufactured by melt-kneading each component using apparatuses, such as a kneader, a mixing roll, a Banbury mixer, a single screw extruder, a twin screw extruder, for example.

  Examples of the shape of the heat insulating member of the present invention include a sheet shape (including a film shape), a plate shape, a tube shape, a column shape, a cone shape, and a frustum shape. In addition to the rod shape and the fiber shape, the tube shape and the columnar shape are irregular shapes such as a prismatic shape such as a triangle or a square, a semicircle, an L shape, a T shape, a U shape, a mountain shape, or a combination thereof. Such shapes may also be included. The columnar shape, the conical shape, and the frustum shape may include a substantially columnar shape such as a capsule shape and a bullet shape, a substantially conical shape, and a substantially frustum shape. The outside of the heat insulating member typically has the above-mentioned shape, but the inside thereof may be hollow or contain depending on the application. The heat insulating member of the present invention may constitute a part of a composite molded product (such as a skin layer of the composite molded product) with another resin, film, metal, or the like.

  The heat insulating member of the present invention can be produced by molding the resin composition. Examples of the molding method include a method of melt-molding a resin composition such as an extrusion molding method, a compression molding method, a blow molding method, a vacuum molding method, and an injection molding method; Examples thereof include a molding method and a so-called solution coating method in which a liquid (solution, emulsion, etc.) containing a resin composition is applied to a support and the coating film is dried. With these molding methods, the above-described various shapes of heat insulating members can be manufactured.

  Among the heat insulating members, when forming a heat insulating member having adhesiveness (for example, an adhesive heat insulating member such as an adhesive heat insulating sheet, a heat insulating sealing member), a molding method by hot melt coating or solution coating is preferable.

Examples of the extrusion molding method include a method using a die (lamination method, coextrusion method, etc.), an inflation method (coextrusion method, etc.), and the like.
In the method using a die, for example, the resin composition is melt-kneaded in a melt extruder, and the molten resin composition is extruded from a die attached to the extruder into a desired shape such as a sheet, and extruded. The heat insulating member of the present invention can be produced by cooling the molded product. Examples of the die include a T die, a coat hanger die, and other known dies. The melt extrusion temperature in the extrusion molding is usually 120 ° C to 300 ° C. The extrusion molding method is suitable as a method for producing a plate-like (sheet-like or film-like) heat insulating member.

  In the injection molding method, for example, the heat insulating member of the present invention can be produced by melting the resin composition in an injection molding machine, injecting the molten composition into a mold having a desired shape, and cooling. . In the injection molding method, a heat insulating member made of the resin composition alone used in the present invention can be formed, or a heat insulating member combined with other resin, film, metal, or the like can be formed. In the case of producing a composite molded product with other resin, film, metal, etc., for example, an insert method, a two-color method, a core back method, a sandwich method, and the like can be mentioned. The melt injection temperature in injection molding is usually 140 ° C to 300 ° C. The injection molding method is suitable as a method for producing a heat insulating member having a desired three-dimensional shape (for example, a tube shape, a column shape, a sheet shape, or the like). In particular, it is suitable for producing a columnar molded body having a partially different diameter size or a composite molded body having a heat insulating member only on a part of the surface of the support.

  As a forming method by the hot melt coating, a general method used for manufacturing a film-like or sheet-like member can be used. Specifically, for example, the resin composition is prepared by melt-kneading, a support film or a support sheet made of a heat-resistant material such as polyethylene terephthalate, or a flat coater or roll such as a steel belt, a roll coater, A heat insulating member can be manufactured by applying a melt of the resin composition using a die coater, a comma coater, or the like and cooling it.

  As a forming method by the solution coating, a general method used for manufacturing a film-like or sheet-like member can be used. Specifically, for example, a bar coater, a roll coater, a die coater, a comma coater or the like is used on a support film or a support sheet made of a heat-resistant material such as polyethylene terephthalate, or a flat plate or roll such as a steel belt. A heat insulating member can be produced by casting a liquid (for example, a solution, an emulsion, etc.) containing the composition and removing the solvent by drying. Note that the support and the obtained heat insulating member may be used after being peeled off, or may be used integrally without being peeled off.

  Examples of the solvent used in the solution coating method include toluene, ethyl acetate, ethylbenzene, methylene chloride, chloroform, tetrahydrofuran, methyl ethyl ketone, dimethyl sulfoxide, toluene-ethanol mixed solvent, and the like. Among these, toluene, ethylbenzene, ethyl acetate, and methyl ethyl ketone are preferable.

  In the case of producing a heat insulating member having adhesiveness, in particular, an adhesive heat insulating sheet, a sheet-like member can be prepared by the above hot melt coating or solution coating. From the viewpoint of stabilizing the dispersion state of the hollow particles, A molding method by coating is preferred.

  The heat insulating member of the present invention is excellent not only in a heat insulating function but also in a heat insulating function, a heat retaining effect, and the like, and is also excellent in soundproofing, sound absorbing property, light reflecting performance, insulating property and the like. Further, the heat insulating member of the present invention is improved in light weight and dimensional stability. Moreover, since there is little destruction of a hollow particle, it can utilize as a heat insulation protective layer and a temperature-sensitive improvement layer as a molded object for injection insert molding, a film, a film sheet for vacuum forming, etc. Moreover, if the formulation which has adhesiveness is selected, it can be used as, for example, an adhesive heat insulating member such as an adhesive tape, a heat insulating sealant member, or the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by them. Various physical properties in Examples and Comparative Examples were measured or evaluated by the following methods.

(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the (meth) acrylic block copolymer were determined by gel permeation chromatography as standard polystyrene equivalent molecular weight.
-Equipment: GPC equipment "HLC-8020" manufactured by Tosoh Corporation
Column: “TSKgel GMHXL”, “G4000HXL” and “G5000HXL” manufactured by Tosoh Corporation are connected in series. Eluent: tetrahydrofuran Eluent flow rate: 1.0 ml / min Column temperature: 40 ° C.
・ Detection method: Differential refractive index (RI)

(2) Composition ratio (mass ratio) of each polymer block in the (meth) acrylic block copolymer
^It was determined by ¹ H-NMR measurement.
・ Device: JEOL Nuclear Magnetic Resonance Device “JNM-LA400”
・ Deuterated solvent: Deuterated chloroform

(3) Glass transition temperature (Tg) of each polymer block in the (meth) acrylic block copolymer
In the curve obtained by DSC measurement using a DSC measuring apparatus (DSC-822) manufactured by METTLER at a temperature increase rate of 10 ° C./min, the extrapolation start temperature (Tgi) is the glass transition temperature (Tg). It was.

(4) Melt flow rate (MFR) of (meth) acrylic block copolymer
According to JIS K 7210, the melt flow rate (MFR) in 230 degreeC and a 2.16kg load was measured.

(5) Kneading workability The (meth) acrylic block copolymer and 60 ml of the hollow particles having the mixing ratios of the examples and comparative examples were placed in a kneader (labor plast mill, manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 230 ° C. and 100 rpm. Whether or not kneading can be carried out for 5 minutes was determined according to the following criteria. The measured value of specific gravity measured by the method described below was compared with the value obtained from the calculation, and when the measured value was large, it was determined that hollow particles were crushed.
Kneading possible: ○
Kneading is possible, but hollow particles are crushed: △
Exceeds torque upper limit and cannot be kneaded: ×

(6) Adhesiveness The resin composition obtained by melting and kneading for 5 minutes in a lab plast mill under the conditions of 100 rpm and 230 ° C. with the formulation shown in Table 2, using a press molding machine under the conditions of 230 ° C. The probe tack of a 300 μm-thick press sheet obtained in the above was measured in accordance with ASTM D 2979 and used as an index of adhesion. Probe diameter 5 mm
Measurement load 17.4g / 5mmφ (9.79kPa)
Contact time 1 second Peeling speed 10 mm / sec
Measuring instrument Probe Material Analyzer PMA-1000 (manufactured by Chem Instruments)
Adhesive strength measured under the above conditions is 50 g or more: ○
Adhesive strength measured under the above conditions is less than 50 g: x

(7) Calculated specific gravity The calculated specific gravity (Dcal) was determined as follows.
Dcal = (Wa + Wb) / (Wa / Da + Wb / Db)
Dcal: Calculated specific gravity of composition Wa: Mass ratio of (meth) acrylic block copolymer Wb: Mass ratio of hollow particles Da: Specific gravity of (meth) acrylic block copolymer Db: Specific gravity of hollow particles

(8) Specific gravity The resin composition obtained by kneading under the above condition (5) was preheated at 230 ° C. for 90 seconds using a hot press molding machine, and then pressurized at 8.8 MPa for 1 minute, and 5 cm × A press sheet of 5 cm × 3 mm was produced, and the specific gravity was measured in accordance with ISO 1183.

(9) Temperature Sensitivity In a constant temperature room of 23 ° C., 10 panelists touch the sheet obtained in the above (8) with their hands and judge by the number of people who feel warm.
Warm: A warmth different from the sheet made of the triblock copolymer (I) obtained in the same manner as in the above (8) is felt.
Cold: Feels the same coldness as the sheet made of the triblock copolymer (I) obtained in the same manner as in the above (8) ○: 5 or more Δ: 1-4 people ×: 0 people

[Synthesis example]
In the synthesis examples shown below, the compound used was dried and purified by a conventional method and degassed with nitrogen. Moreover, the transfer and supply of the compounds were performed in a nitrogen atmosphere.

[Synthesis Examples 1 to 6] Acrylic block copolymers (I) to (VI)
In the presence of isobutylbis (2,6-di-tert-butylphenoxy) aluminum, sec-butyllithium is used as a polymerization initiator, and monomers corresponding to each block are sequentially added in toluene for anion living polymerization. Acrylic block copolymers (I) to (VI) were obtained by a devolatilizing twin-screw extruder after synthesis by the method and removal of the used aluminum and lithium components. Table 1 shows the details of the acrylic block copolymers (I) to (VI).

[Examples 1-7, Reference Examples 1-3 and Comparative Examples 1-2]
Using the acrylic block copolymers (I) to (VI) prepared in Synthesis Examples 1 to 6 and Glass Bubbles (manufactured by S60HS, 3M, average particle diameter 30 μm, porosity 76%), the above (5) The kneadability, tackiness, specific gravity, and temperature sensitivity were evaluated according to the test conditions (9) to (9). The results are shown in Table 2.

  From Table 2, in the blends of Examples 1 to 7, a composition excellent in melt kneadability is obtained based on the excellent fluidity of the (meth) acrylic block copolymer, and the specific gravity matches the calculated specific gravity. Therefore, it can be said that the hollow particles are not crushed. Moreover, it has adhesiveness in the mixing | blending of Examples 4-6, and can be used as an adhesive heat insulating member.

  In Reference Example 2 and Reference Example 3, the kneadability is slightly inferior, the specific gravity of the obtained resin composition is larger than the calculated specific gravity, and it can be said that the hollow particles are at least partially broken. On the other hand, as in Comparative Example 1, when the added amount of the hollow particles exceeded the range of the present invention, kneading could not be performed and a resin composition could not be obtained.

Claims (5)

(Meth) acrylic block copolymer is a resin composition containing 50 to 70 % by mass and hollow particles 30 to 50 % by mass ,
The (meth) acrylic block copolymer has at least one polymer block (A) mainly composed of (meth) acrylic acid ester having a glass transition temperature (Tg) of 25 ° C. or higher, and a Tg of less than 25 ° C. A polymer block (B) mainly composed of (meth) acrylic acid ester, and the total of the polymer blocks (A) with respect to 100% by mass of the (meth) acrylic block copolymer The resin composition whose mass is 5-45 mass% and the total mass of the said polymer block (B) is 55-95 mass% . The resin composition according to claim 1 , wherein the (meth) acrylic block copolymer has a portion in which the polymer block (A), the polymer block (B), and the polymer block (A) are bonded in this order. . A heat insulating member obtained from the resin composition according to claim 1 . A heat-insulating sealant member obtained from the resin composition according to claim 1 . The adhesive heat insulation member obtained from the resin composition of Claim 1 or 2 .