WO2018030455A1 - Resin composition - Google Patents
Resin composition Download PDFInfo
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- WO2018030455A1 WO2018030455A1 PCT/JP2017/028886 JP2017028886W WO2018030455A1 WO 2018030455 A1 WO2018030455 A1 WO 2018030455A1 JP 2017028886 W JP2017028886 W JP 2017028886W WO 2018030455 A1 WO2018030455 A1 WO 2018030455A1
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- resin
- resin composition
- functional group
- repeating unit
- group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
Definitions
- the present invention relates to a resin composition having excellent thermal stability.
- Patent Document 1 a resin composition highly filled with inorganic particles has been melt-molded.
- melt molding in order to uniformly disperse inorganic particles in a resin, kneading is usually performed at a temperature equal to or higher than the melting point of the resin.
- the surface state is not stable when the particle surface is active or the acid basicity is biased to one side. For this reason, during kneading of a resin having a functional group such as polyester in the main chain and inorganic particles, the molecular weight is lowered due to decomposition of the main chain in the resin, and desired physical properties may not be obtained.
- the present invention aims to provide a stable resin composition independent of the properties of inorganic particles.
- the object of the present invention has been achieved by the following.
- a resin (A) containing a repeating unit having a functional group in the main chain, a resin (B) consisting of a repeating unit having no functional group in the main chain, and inorganic particles (C) are contained at least one each.
- Resin composition (2) The resin composition as described in 1 above, wherein the functional group is an ester group, an amide group, an imide group, a carbonate group, an ether group, or a thioether group.
- the resin composition as described in 1 to 3 wherein at least one of the resin (A) and the resin (B) is a biodegradable resin.
- a resin molded body comprising the resin composition as described in any one of 1 to 5 above.
- the resin composition of the present invention comprises a resin (A) containing a repeating unit having a functional group in the main chain, a resin (B) consisting of a repeating unit having no functional group in the main chain, and inorganic particles (C). It is characterized by containing at least one of each.
- the functional group in the present invention refers to a group that decomposes depending on the properties of the inorganic particles, and typical groups include ester groups, amide groups, imide groups, carbonate groups, ether groups, and thioether groups.
- the resin containing a repeating unit having a functional group of the present invention include a polyester resin, a polyamide resin, a polyimide resin, and a polycarbonate resin.
- polyester resin of the present invention examples include polyethylene terephthalate, polybutylene terephthalate (manufactured by Duranex (registered trademark) Polyplastics), polyethylene naphthalate (manufactured by Teonex (registered trademark) Teijin), polylactic acid (Lacia (registered trademark)).
- Polyamide resins such as Mitsui Chemicals, Ecodia (registered trademark) Toray, and Terramac (registered trademark) Unitika), etc. 6-nylon, 6,6-nylon (Amilan (registered trademark) Toray), etc.
- polyimide resin As a polyimide resin, commercially available products such as Upilex (registered trademark, manufactured by Ube Industries), Besbell (registered trademark, manufactured by DuPont), Imidaroy (registered trademark, manufactured by Kyocera), etc., carbonate resin, Panlite (registered) Trademark, manufactured by Teijin Limited), polybutylene succinate (registered trademark, Biono) Manufactured by Les Showa Denko Co.), polyether resins, polyacetal, polyphenylene oxide, polyether ketone, polyether ether ketone, polythioether like.
- Upilex registered trademark, manufactured by Ube Industries
- Besbell registered trademark, manufactured by DuPont
- Imidaroy registered trademark, manufactured by Kyocera
- carbonate resin Panlite (registered) Trademark, manufactured by Teijin Limited)
- polybutylene succinate registered trademark, Biono) Manufactured by Les Showa Denko Co.
- polyether resins polyacetal
- the resin containing a repeating unit having a functional group in the main chain of the present invention may contain a repeating unit having no functional group, and the repeating unit having a functional group contained in the main chain is composed of all repeating units. 30 mol% or more, preferably 50 mol% or more is contained.
- Resin (B) made of a repeating unit having no functional group in the main chain examples include polyolefin resin, cycloolefin resin, cellulose ester resin, cellulose ether resin, polyvinylidene chloride resin, polyvinyl chloride resin, ABS resin, acrylic resin, etc. Can be mentioned.
- Resin consisting of a repeating unit having no functional group in the main chain is characterized by substantially not containing a repeating unit having a functional group in the main chain, but within a range not impeding the effects of the present invention, for example, You may include the repeating unit which has a functional group in a principal chain within 10 mol%.
- At least one of the resin (A) and the resin (B) of the present invention is preferably a biodegradable resin.
- the biodegradable resin means a resin that is completely consumed by microorganisms in the natural world and is finally decomposed into water and carbon dioxide. Specific examples include polylactic acid, polycaprolactone, polybutylene succinate, polybutylene adipate, polyethylene succinate, and cellulose ester.
- the inorganic particles of the present invention are not particularly limited, and examples thereof include calcium carbonate, titanium oxide, silica, clay, talc, kaolin, aluminum hydroxide, calcium sulfate, barium sulfate, mica, zinc oxide, dolomite, glass fiber, and hollow glass. Can be mentioned. Preferably it is calcium carbonate.
- the shape of the inorganic particles can be any of granular, acicular, and flat. An average particle diameter of 0.01 to 20 ⁇ m can be appropriately used.
- the resin composition of the present invention comprises a resin (A) containing a repeating unit having a functional group in the main chain, a resin (B) consisting of a repeating unit having no functional group in the main chain, and inorganic particles (C).
- Each resin contains at least one kind, but the resin (A) containing a repeating unit having a functional group in the main chain is 3 to 80% by mass, preferably 5 to 50% by mass, and has no functional group in the main chain.
- the resin (B) composed of repeating units is 0.1 to 80% by mass, preferably 0.5 to 50% by mass, and the inorganic particles (C) are 30 to 95% by mass, preferably 50 to 50% by mass. 90% by mass. In the preferred range, the effects of the present invention can be obtained more.
- (A), (B) and (C) of the present invention may be mixed and heated and kneaded at the same time, but (B) and (C) are first mixed and kneaded, and then (A) is mixed. You can also. It is also possible to coat (C) with (B) and then mix and knead with (A) after coating the surface with a method such as spray drying.
- the coating film thickness is preferably in the range of 5 to 40% of the particle size. For example, in the case of inorganic particles having an average particle diameter of 5 ⁇ m, it is 0.025 to 2 ⁇ m. The film thickness can be appropriately adjusted depending on the amount to be sprayed.
- two or more components (A), (B), and (C) may be contained, and in addition to the components A), (B), and (C), a lubricant,
- a lubricant one or more auxiliary agents selected from among antioxidants, ultraviolet absorbers, coloring pigments, dispersants, compatibilizers, antistatic agents, flame retardants and the like can be added within a range that does not contradict the purpose. .
- the resin composition of the present invention is used as a structure and requires strength, it is also preferable to contain reinforcing fibers such as cellulose nanofibers.
- Cellulose nanofibers having a width of 4 to 100 nm and a length of 5 to 500 ⁇ m can be preferably used. The content can be appropriately determined depending on the application.
- the resin composition of the present invention can be applied to the use of ordinary thermoplastic compositions such as sheet and injection molding. Moreover, it can be set as an environmentally friendly resin composition by selecting biodegradable resin for (A) and (B).
- polylactic acid Lacia (registered trademark) H-100 manufactured by Mitsui Chemicals, Inc.
- cellulose acetate butyrate CAB-551 manufactured by Eastman Chemical Co., Ltd.
- average particle size d50
- Example 2 cellulose acetate butyrate and calcium carbonate were previously kneaded and then polylactic acid was added and further kneaded. The time when polylactic acid was charged was set to zero time.
- Example 3 cellulose acetate butyrate coated with calcium carbonate using a fluidized bed granulation dryer was used.
Abstract
The object of the present invention is to provide a resin composition which is stable regardless of the properties of inorganic particles contained therein. The object is achieved by a resin composition containing at least each one of (A) a resin which contains a repeating unit having a functional group in the main chain thereof, (B) a resin composed of a repeating unit not having a functional group in the main chain thereof, and (C) inorganic particles.
Description
本発明は、 熱安定性に優れた樹脂組成物に関する。
The present invention relates to a resin composition having excellent thermal stability.
従来より、無機粒子を高充填した樹脂組成物を、溶融成形することが行われてきた（特許文献１）。溶融成形では、無機粒子を樹脂に均一に分散するため樹脂の融点以上の温度で混練することが通常行われる。
Conventionally, a resin composition highly filled with inorganic particles has been melt-molded (Patent Document 1). In melt molding, in order to uniformly disperse inorganic particles in a resin, kneading is usually performed at a temperature equal to or higher than the melting point of the resin.
しかしながら無機粒子によっては、粒子表面が活性であったり酸塩基性が一方に偏ったりと、表面状態が安定ではない。そのためポリエステル等の官能基を主鎖に有する樹脂と無機粒子を混練している最中に樹脂中の主鎖の分解により、分子量が低下して、所望の物性の得られないことがあった。
However, depending on the inorganic particles, the surface state is not stable when the particle surface is active or the acid basicity is biased to one side. For this reason, during kneading of a resin having a functional group such as polyester in the main chain and inorganic particles, the molecular weight is lowered due to decomposition of the main chain in the resin, and desired physical properties may not be obtained.
本発明は、無機粒子の性質によらない安定した樹脂組成物の提供を目的とする。
The present invention aims to provide a stable resin composition independent of the properties of inorganic particles.
本発明の前記目的は、下記によって達成された。
The object of the present invention has been achieved by the following.
（１）主鎖に官能基を有する繰り返し単位を含む樹脂（Ａ）、主鎖に官能基を有していない繰り返し単位からなる樹脂（Ｂ）及び無機粒子（Ｃ）を、それぞれ少なくとも一種含有する樹脂組成物。
（２）前記官能基が、エステル基、アミド基、イミド基、カーボネート基、エーテル基、チオエーテル基である前記１記載の樹脂組成物。
（３）前記無機粒子の含有量が３０質量％以上である前記１または２記載の樹脂組成物。
（４）前記樹脂（Ａ）、樹脂（Ｂ）の少なくとも一方が生分解性樹脂である前記１～３記載の樹脂組成物。
（５）セルロースナノファイバーを含有する前記１～４いずれかに記載の樹脂組成物。
（６）前記１～５いずれかに記載の樹脂組成物からなる樹脂成形体。 (1) A resin (A) containing a repeating unit having a functional group in the main chain, a resin (B) consisting of a repeating unit having no functional group in the main chain, and inorganic particles (C) are contained at least one each. Resin composition.
(2) The resin composition as described in 1 above, wherein the functional group is an ester group, an amide group, an imide group, a carbonate group, an ether group, or a thioether group.
(3) The resin composition as described in 1 or 2 above, wherein the content of the inorganic particles is 30% by mass or more.
(4) The resin composition as described in 1 to 3, wherein at least one of the resin (A) and the resin (B) is a biodegradable resin.
(5) The resin composition as described in any one of 1 to 4 above, which contains cellulose nanofibers.
(6) A resin molded body comprising the resin composition as described in any one of 1 to 5 above.
（２）前記官能基が、エステル基、アミド基、イミド基、カーボネート基、エーテル基、チオエーテル基である前記１記載の樹脂組成物。
（３）前記無機粒子の含有量が３０質量％以上である前記１または２記載の樹脂組成物。
（４）前記樹脂（Ａ）、樹脂（Ｂ）の少なくとも一方が生分解性樹脂である前記１～３記載の樹脂組成物。
（５）セルロースナノファイバーを含有する前記１～４いずれかに記載の樹脂組成物。
（６）前記１～５いずれかに記載の樹脂組成物からなる樹脂成形体。 (1) A resin (A) containing a repeating unit having a functional group in the main chain, a resin (B) consisting of a repeating unit having no functional group in the main chain, and inorganic particles (C) are contained at least one each. Resin composition.
(2) The resin composition as described in 1 above, wherein the functional group is an ester group, an amide group, an imide group, a carbonate group, an ether group, or a thioether group.
(3) The resin composition as described in 1 or 2 above, wherein the content of the inorganic particles is 30% by mass or more.
(4) The resin composition as described in 1 to 3, wherein at least one of the resin (A) and the resin (B) is a biodegradable resin.
(5) The resin composition as described in any one of 1 to 4 above, which contains cellulose nanofibers.
(6) A resin molded body comprising the resin composition as described in any one of 1 to 5 above.
本発明によれば、無機粒子の性質の影響を受けにくい安定した樹脂組成物を得ることができる。
According to the present invention, a stable resin composition that is hardly affected by the properties of inorganic particles can be obtained.
以下、本発明の実施形態について詳細に述べる。
本発明の樹脂組成物は、主鎖に官能基を有する繰り返し単位を含む樹脂（Ａ）、主鎖に官能基を有していない繰り返し単位からなる樹脂（Ｂ）及び無機粒子（Ｃ）を、それぞれ少なくとも一種含有することを特徴とする。 Hereinafter, embodiments of the present invention will be described in detail.
The resin composition of the present invention comprises a resin (A) containing a repeating unit having a functional group in the main chain, a resin (B) consisting of a repeating unit having no functional group in the main chain, and inorganic particles (C). It is characterized by containing at least one of each.
本発明の樹脂組成物は、主鎖に官能基を有する繰り返し単位を含む樹脂（Ａ）、主鎖に官能基を有していない繰り返し単位からなる樹脂（Ｂ）及び無機粒子（Ｃ）を、それぞれ少なくとも一種含有することを特徴とする。 Hereinafter, embodiments of the present invention will be described in detail.
The resin composition of the present invention comprises a resin (A) containing a repeating unit having a functional group in the main chain, a resin (B) consisting of a repeating unit having no functional group in the main chain, and inorganic particles (C). It is characterized by containing at least one of each.
＜主鎖に官能基を有する繰り返し単位を含む樹脂（Ａ）＞
本発明でいう官能基とは、無機粒子の性質によって分解する基をいい、エステル基、アミド基、イミド基、カーボネート基、エーテル基、チオエーテル基が典型性な基としてあげられる。
本発明の官能基を有する繰り返し単位を含む樹脂としては、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリカーボネート樹脂等が挙げられる。 <Resin (A) containing a repeating unit having a functional group in the main chain>
The functional group in the present invention refers to a group that decomposes depending on the properties of the inorganic particles, and typical groups include ester groups, amide groups, imide groups, carbonate groups, ether groups, and thioether groups.
Examples of the resin containing a repeating unit having a functional group of the present invention include a polyester resin, a polyamide resin, a polyimide resin, and a polycarbonate resin.
本発明でいう官能基とは、無機粒子の性質によって分解する基をいい、エステル基、アミド基、イミド基、カーボネート基、エーテル基、チオエーテル基が典型性な基としてあげられる。
本発明の官能基を有する繰り返し単位を含む樹脂としては、ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリカーボネート樹脂等が挙げられる。 <Resin (A) containing a repeating unit having a functional group in the main chain>
The functional group in the present invention refers to a group that decomposes depending on the properties of the inorganic particles, and typical groups include ester groups, amide groups, imide groups, carbonate groups, ether groups, and thioether groups.
Examples of the resin containing a repeating unit having a functional group of the present invention include a polyester resin, a polyamide resin, a polyimide resin, and a polycarbonate resin.
本発明のポリエステル樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート（ジュラネックス（登録商標）ポリプラスチックス社製）、ポリエチレンナフタレート（テオネックス（登録商標）帝人社製）、ポリ乳酸（レイシア（登録商標）三井化学社製、エコディア（登録商標）東レ社製、テラマック（登録商標）ユニチカ社製）等、ポリアミド樹脂としては、６－ナイロン、６，６－ナイロン（アミラン（登録商標）東レ社製）等、ポリイミド樹脂としては、市販品としてユーピレックス（登録商標、宇部興産社製）、ベスベル（登録商標、デュポン社製）、イミダロイ（登録商標、京セラ社製）等、カーボネート樹脂としては、パンライト（登録商標、帝人社製）、ポリブチレンサクシネート（登録商標 ビオノーレ 昭和電工社製）、ポリエーテル樹脂としては、ポリアセタール、ポリフェニレンオキサイド、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリチオエーテル等を挙げることができる。
Examples of the polyester resin of the present invention include polyethylene terephthalate, polybutylene terephthalate (manufactured by Duranex (registered trademark) Polyplastics), polyethylene naphthalate (manufactured by Teonex (registered trademark) Teijin), polylactic acid (Lacia (registered trademark)). Polyamide resins such as Mitsui Chemicals, Ecodia (registered trademark) Toray, and Terramac (registered trademark) Unitika), etc. 6-nylon, 6,6-nylon (Amilan (registered trademark) Toray), etc. As a polyimide resin, commercially available products such as Upilex (registered trademark, manufactured by Ube Industries), Besbell (registered trademark, manufactured by DuPont), Imidaroy (registered trademark, manufactured by Kyocera), etc., carbonate resin, Panlite (registered) Trademark, manufactured by Teijin Limited), polybutylene succinate (registered trademark, Biono) Manufactured by Les Showa Denko Co.), polyether resins, polyacetal, polyphenylene oxide, polyether ketone, polyether ether ketone, polythioether like.
本発明の主鎖に官能基を有する繰り返し単位を含む樹脂は、官能基を有していない繰り返し単位を含んでいてもよく、主鎖に含まれる官能基を有する繰り返し単位は、全繰り返し単位の３０モル％以上、好ましくは５０モル％以上含まれる。
The resin containing a repeating unit having a functional group in the main chain of the present invention may contain a repeating unit having no functional group, and the repeating unit having a functional group contained in the main chain is composed of all repeating units. 30 mol% or more, preferably 50 mol% or more is contained.
＜主鎖に官能基を有していない繰り返し単位からなる樹脂（Ｂ）＞
本発明の官能基を有していない繰り返し単位からなる樹脂としては、ポリオレフィン樹脂、シクロオレフィン樹脂、セルロースエステル樹脂、セルロースエーテル樹脂、ポリ塩化ビニリデン樹脂、ポリ塩化ビニル樹脂等、ＡＢＳ樹脂、アクリル樹脂等を挙げることができる。 <Resin (B) made of a repeating unit having no functional group in the main chain>
Examples of the resin composed of a repeating unit having no functional group of the present invention include polyolefin resin, cycloolefin resin, cellulose ester resin, cellulose ether resin, polyvinylidene chloride resin, polyvinyl chloride resin, ABS resin, acrylic resin, etc. Can be mentioned.
本発明の官能基を有していない繰り返し単位からなる樹脂としては、ポリオレフィン樹脂、シクロオレフィン樹脂、セルロースエステル樹脂、セルロースエーテル樹脂、ポリ塩化ビニリデン樹脂、ポリ塩化ビニル樹脂等、ＡＢＳ樹脂、アクリル樹脂等を挙げることができる。 <Resin (B) made of a repeating unit having no functional group in the main chain>
Examples of the resin composed of a repeating unit having no functional group of the present invention include polyolefin resin, cycloolefin resin, cellulose ester resin, cellulose ether resin, polyvinylidene chloride resin, polyvinyl chloride resin, ABS resin, acrylic resin, etc. Can be mentioned.
具体的には、ポリエチレン、ポリプロピレン、ポリシクロオレフィン、セルロースプロピオネート、セルロースブチレート、セルロースアセテートプロピオネート（ＣＡＰエーストマンケミカル社製）、セルロースアセテートブチレート（ＣＡＢイーストマンケミカル社製）、ポリ塩化ビニリデン－塩化ビニル共重合体等を挙げることができる。
Specifically, polyethylene, polypropylene, polycycloolefin, cellulose propionate, cellulose butyrate, cellulose acetate propionate (manufactured by CAP Eastman Chemical), cellulose acetate butyrate (manufactured by CAB Eastman Chemical), poly And vinylidene chloride-vinyl chloride copolymer.
主鎖に官能基を有していない繰り返し単位からなる樹脂は、実質的に主鎖に官能基を有する繰り返し単位を含まないことを特徴とするが、本発明の効果を妨げない範囲で、例えば１０モル％以内で主鎖に官能基を有する繰り返し単位を含んでもよい。
Resin consisting of a repeating unit having no functional group in the main chain is characterized by substantially not containing a repeating unit having a functional group in the main chain, but within a range not impeding the effects of the present invention, for example, You may include the repeating unit which has a functional group in a principal chain within 10 mol%.
本発明の樹脂（Ａ）、樹脂（Ｂ）の少なくとも一方は、生分解性樹脂であることが好ましい。ここで生分解性樹脂とは、自然界の微生物によって完全に消費され最終的に水と二酸化炭素に分解される樹脂をいう。具体的には、ポリ乳酸、ポリカプロラクトン、ポリブチレンサクシネート、ポリブチレンアジペート、ポリエチレンサクシネート、セルロースエステル等を挙げることができる。
At least one of the resin (A) and the resin (B) of the present invention is preferably a biodegradable resin. Here, the biodegradable resin means a resin that is completely consumed by microorganisms in the natural world and is finally decomposed into water and carbon dioxide. Specific examples include polylactic acid, polycaprolactone, polybutylene succinate, polybutylene adipate, polyethylene succinate, and cellulose ester.
＜無機粒子（Ｃ）＞
本発明の無機粒子は特に限定されないが、例えば炭酸カルシウム、酸化チタン、シリカ、クレー、タルク、カオリン、水酸化アルミニウム、硫酸カルシウム、硫酸バリウム、マイカ、酸化亜鉛、ドロマイト、ガラス繊維、中空ガラス等を挙げることができる。好ましくは炭酸カルシウムである。 <Inorganic particles (C)>
The inorganic particles of the present invention are not particularly limited, and examples thereof include calcium carbonate, titanium oxide, silica, clay, talc, kaolin, aluminum hydroxide, calcium sulfate, barium sulfate, mica, zinc oxide, dolomite, glass fiber, and hollow glass. Can be mentioned. Preferably it is calcium carbonate.
本発明の無機粒子は特に限定されないが、例えば炭酸カルシウム、酸化チタン、シリカ、クレー、タルク、カオリン、水酸化アルミニウム、硫酸カルシウム、硫酸バリウム、マイカ、酸化亜鉛、ドロマイト、ガラス繊維、中空ガラス等を挙げることができる。好ましくは炭酸カルシウムである。 <Inorganic particles (C)>
The inorganic particles of the present invention are not particularly limited, and examples thereof include calcium carbonate, titanium oxide, silica, clay, talc, kaolin, aluminum hydroxide, calcium sulfate, barium sulfate, mica, zinc oxide, dolomite, glass fiber, and hollow glass. Can be mentioned. Preferably it is calcium carbonate.
無機粒子の形状は、粒状、針状、偏平状いずれも使用することができる。平均粒径は、０．０１～２０μｍのものを適宜使用することができる。
The shape of the inorganic particles can be any of granular, acicular, and flat. An average particle diameter of 0.01 to 20 μm can be appropriately used.
＜本発明の樹脂組成物＞
本発明の樹脂組成物は、主鎖に官能基を有する繰り返し単位を含む樹脂（Ａ）、主鎖に官能基を有していない繰り返し単位からなる樹脂（Ｂ）及び無機粒子（Ｃ）を、それぞれ少なくとも一種含有するが、主鎖に官能基を有する繰り返し単位を含む樹脂（Ａ）が３～８０質量％、好ましくは、５～５０質量％であり、主鎖に官能基を有していない繰り返し単位からなる樹脂（Ｂ）は、０．１～８０質量％、好ましくは０．５～５０質量％であり、無機粒子（Ｃ）は、３０～９５質量％であり、好ましくは、５０～９０質量％である。好ましい範囲では、本発明の効果がより得られる。 <Resin composition of the present invention>
The resin composition of the present invention comprises a resin (A) containing a repeating unit having a functional group in the main chain, a resin (B) consisting of a repeating unit having no functional group in the main chain, and inorganic particles (C). Each resin contains at least one kind, but the resin (A) containing a repeating unit having a functional group in the main chain is 3 to 80% by mass, preferably 5 to 50% by mass, and has no functional group in the main chain. The resin (B) composed of repeating units is 0.1 to 80% by mass, preferably 0.5 to 50% by mass, and the inorganic particles (C) are 30 to 95% by mass, preferably 50 to 50% by mass. 90% by mass. In the preferred range, the effects of the present invention can be obtained more.
本発明の樹脂組成物は、主鎖に官能基を有する繰り返し単位を含む樹脂（Ａ）、主鎖に官能基を有していない繰り返し単位からなる樹脂（Ｂ）及び無機粒子（Ｃ）を、それぞれ少なくとも一種含有するが、主鎖に官能基を有する繰り返し単位を含む樹脂（Ａ）が３～８０質量％、好ましくは、５～５０質量％であり、主鎖に官能基を有していない繰り返し単位からなる樹脂（Ｂ）は、０．１～８０質量％、好ましくは０．５～５０質量％であり、無機粒子（Ｃ）は、３０～９５質量％であり、好ましくは、５０～９０質量％である。好ましい範囲では、本発明の効果がより得られる。 <Resin composition of the present invention>
The resin composition of the present invention comprises a resin (A) containing a repeating unit having a functional group in the main chain, a resin (B) consisting of a repeating unit having no functional group in the main chain, and inorganic particles (C). Each resin contains at least one kind, but the resin (A) containing a repeating unit having a functional group in the main chain is 3 to 80% by mass, preferably 5 to 50% by mass, and has no functional group in the main chain. The resin (B) composed of repeating units is 0.1 to 80% by mass, preferably 0.5 to 50% by mass, and the inorganic particles (C) are 30 to 95% by mass, preferably 50 to 50% by mass. 90% by mass. In the preferred range, the effects of the present invention can be obtained more.
本発明の（Ａ）、（Ｂ）、（Ｃ）は同時に混合して加熱、混練してもよいが、（Ｂ）と（Ｃ）を先に混合、混練した後に（Ａ）を混合することもできる。また（Ｃ）に（Ｂ）をスプレードライ等の方法により表面にコーティングした後、（Ａ）と混合、混練することも可能である。その場合コーティング膜厚は粒径の５～４０％の範囲であることが好ましい。例えば、平均粒径が５μｍの無機粒子であれば、０．０２５～２μｍである。膜厚は、スプレーする量によって適宜調整することができる。
(A), (B) and (C) of the present invention may be mixed and heated and kneaded at the same time, but (B) and (C) are first mixed and kneaded, and then (A) is mixed. You can also. It is also possible to coat (C) with (B) and then mix and knead with (A) after coating the surface with a method such as spray drying. In that case, the coating film thickness is preferably in the range of 5 to 40% of the particle size. For example, in the case of inorganic particles having an average particle diameter of 5 μm, it is 0.025 to 2 μm. The film thickness can be appropriately adjusted depending on the amount to be sprayed.
本発明の樹脂組成物においては、（Ａ）、（Ｂ）、（Ｃ）の成分はそれぞれ２種以上含有させてもよく、Ａ）、（Ｂ）、（Ｃ）成分の他に、滑剤、酸化防止剤、紫外線吸収剤、着色用顔料、分散剤、相溶化剤、帯電防止剤、難燃剤等の中から選ばれる１種以上の補助剤を、目的に反しない範囲で添加することができる。
In the resin composition of the present invention, two or more components (A), (B), and (C) may be contained, and in addition to the components A), (B), and (C), a lubricant, One or more auxiliary agents selected from among antioxidants, ultraviolet absorbers, coloring pigments, dispersants, compatibilizers, antistatic agents, flame retardants and the like can be added within a range that does not contradict the purpose. .
本発明の樹脂組成物を構造体として強度の必要な使用をするときは、セルロースナノファイバー等の補強用繊維を含有させることも好ましい。セルロースナノファイバーは、幅４～１００ｎｍ、長さ５～５００μｍのものを好ましく使用することができる。含有量は、用途によって適宜定めることができる
When the resin composition of the present invention is used as a structure and requires strength, it is also preferable to contain reinforcing fibers such as cellulose nanofibers. Cellulose nanofibers having a width of 4 to 100 nm and a length of 5 to 500 μm can be preferably used. The content can be appropriately determined depending on the application.
＜本発明の樹脂組成物の用途＞
本発明の樹脂組成物は、シート、射出成形用途等、通常の熱可塑性組成物の用途に適用することができる。また（Ａ）、（Ｂ）に生分解性樹脂を選択することで環境にやさしい樹脂組成物とすることができる。 <Use of resin composition of the present invention>
The resin composition of the present invention can be applied to the use of ordinary thermoplastic compositions such as sheet and injection molding. Moreover, it can be set as an environmentally friendly resin composition by selecting biodegradable resin for (A) and (B).
本発明の樹脂組成物は、シート、射出成形用途等、通常の熱可塑性組成物の用途に適用することができる。また（Ａ）、（Ｂ）に生分解性樹脂を選択することで環境にやさしい樹脂組成物とすることができる。 <Use of resin composition of the present invention>
The resin composition of the present invention can be applied to the use of ordinary thermoplastic compositions such as sheet and injection molding. Moreover, it can be set as an environmentally friendly resin composition by selecting biodegradable resin for (A) and (B).
以下実施例によって具体的に説明する。
下記の通り（数値は質量％）ポリ乳酸（レイシア（登録商標）Ｈ－１００三井化学社製）、セルロースアセテートブチレート（ＣＡＢ－５５１イーストマンケミカル社製）、平均粒子径（ｄ５０）が１．０μｍで、粒子径５０μｍ以上の粒子を含有しない炭酸カルシウム（ソフトン２２００（登録商標）白石カルシウム製）と、カルシウムステアレート（日油社製）３質量％を、小型二軸押出機（スクリュー径＝ψ２５ｍｍ，Ｌ/Ｄ＝４１、パーカーコーポレーション社製）を使用してスクリュー回転数５０ｒｐｍ、２００℃で混練し、混練開始１分と１０分のトルクを測定、１分からの変化量が±１５％を超えた場合を×、超えない場合を○と判定した。 Examples will be described in detail below.
As shown below (numerical value is%), polylactic acid (Lacia (registered trademark) H-100 manufactured by Mitsui Chemicals, Inc.), cellulose acetate butyrate (CAB-551 manufactured by Eastman Chemical Co., Ltd.), average particle size (d50) is 1. Calcium carbonate (Softon 2200 (registered trademark) manufactured by Shiroishi Calcium Co., Ltd.) and 3% by mass of calcium stearate (manufactured by NOF Corporation) containing no particles having a particle size of 50 μm or more at 0 μm, a small twin screw extruder (screw diameter = ψ25 mm, L / D = 41, manufactured by Parker Corporation), kneaded at a screw speed of 50 rpm and 200 ° C., measured the torque at the start of kneading for 1 minute and 10 minutes, and the variation from 1 minute was ± 15%. The case where it exceeded was judged as x, and the case where it was not exceeded was judged as ○.
下記の通り（数値は質量％）ポリ乳酸（レイシア（登録商標）Ｈ－１００三井化学社製）、セルロースアセテートブチレート（ＣＡＢ－５５１イーストマンケミカル社製）、平均粒子径（ｄ５０）が１．０μｍで、粒子径５０μｍ以上の粒子を含有しない炭酸カルシウム（ソフトン２２００（登録商標）白石カルシウム製）と、カルシウムステアレート（日油社製）３質量％を、小型二軸押出機（スクリュー径＝ψ２５ｍｍ，Ｌ/Ｄ＝４１、パーカーコーポレーション社製）を使用してスクリュー回転数５０ｒｐｍ、２００℃で混練し、混練開始１分と１０分のトルクを測定、１分からの変化量が±１５％を超えた場合を×、超えない場合を○と判定した。 Examples will be described in detail below.
As shown below (numerical value is%), polylactic acid (Lacia (registered trademark) H-100 manufactured by Mitsui Chemicals, Inc.), cellulose acetate butyrate (CAB-551 manufactured by Eastman Chemical Co., Ltd.), average particle size (d50) is 1. Calcium carbonate (Softon 2200 (registered trademark) manufactured by Shiroishi Calcium Co., Ltd.) and 3% by mass of calcium stearate (manufactured by NOF Corporation) containing no particles having a particle size of 50 μm or more at 0 μm, a small twin screw extruder (screw diameter = ψ25 mm, L / D = 41, manufactured by Parker Corporation), kneaded at a screw speed of 50 rpm and 200 ° C., measured the torque at the start of kneading for 1 minute and 10 minutes, and the variation from 1 minute was ± 15%. The case where it exceeded was judged as x, and the case where it was not exceeded was judged as ○.
なお、実施例２ではセルロースアセテートブチレートと炭酸カルシウムとをあらかじめ混練状態にしてその後ポリ乳酸を加えてさらに混練した。ポリ乳酸の投入時を時間ゼロとした。また実施例３ではセルロースアセテートブチレートを炭酸カルシウムに流動層造粒乾燥装置でコーティングを施したものを用いた。
In Example 2, cellulose acetate butyrate and calcium carbonate were previously kneaded and then polylactic acid was added and further kneaded. The time when polylactic acid was charged was set to zero time. In Example 3, cellulose acetate butyrate coated with calcium carbonate using a fluidized bed granulation dryer was used.
Claims (6)
- 主鎖に官能基を有する繰り返し単位を含む樹脂（Ａ）、主鎖に官能基を有していない繰り返し単位からなる樹脂（Ｂ）及び無機粒子（Ｃ）を、それぞれ少なくとも一種含有する樹脂組成物。 Resin composition containing at least one type of resin (A) containing a repeating unit having a functional group in the main chain, resin (B) consisting of a repeating unit having no functional group in the main chain, and inorganic particles (C). .
- 前記官能基が、エステル基、アミド基、イミド基、カーボネート基、エーテル基、チオエーテル基である請求項１記載の樹脂組成物。 The resin composition according to claim 1, wherein the functional group is an ester group, an amide group, an imide group, a carbonate group, an ether group, or a thioether group.
- 前記無機粒子の含有量が３０質量％以上である請求項１または２記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the content of the inorganic particles is 30% by mass or more.
- 前記樹脂（Ａ）、樹脂（Ｂ）の少なくとも一方が生分解性樹脂である請求項１～３記載の樹脂組成物。 The resin composition according to claims 1 to 3, wherein at least one of the resin (A) and the resin (B) is a biodegradable resin.
- セルロースナノファイバーを含有する請求項１～４記載の樹脂組成物。 The resin composition according to claims 1 to 4, comprising cellulose nanofibers.
- 請求項１～５いずれかの項記載の樹脂組成物からなる樹脂成形体。 A resin molded article comprising the resin composition according to any one of claims 1 to 5.
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| WO2020049947A1 (en) * | 2018-09-03 | 2020-03-12 | Dic株式会社 | Additive for cellulose ester resin, and cellulose ester composition |
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