Use of resin compositions, modifiers, and rosin-based resins

Abstract

To provide a polyolefin resin / cellulose composite composition that suppresses the deterioration of mechanical properties and has good moldability. [Solution] A resin composition comprising a polyolefin resin (A) (but not component (C)), cellulose (B), an acid-modified polyolefin resin (C), and a rosin-based resin (D), wherein the acid value of the rosin-based resin (D) is 130 to 320 mgKOH / g, and the weight-average molecular weight (Mw) of the rosin-based resin (D) is 350 to 2,000.

Description

Technical Field

[0001] The present invention relates to the use of a resin composition, a modifier, and a rosin-based resin.

Background Art

[0002] Polyolefin resins are processed into injection-molded products, hollow-molded products, films, sheets, fibers, etc. and are widely used in various applications. On the other hand, since polyolefin resins are inferior in mechanical properties compared to engineering plastics such as super engineering plastics, fiber-reinforced resins in which reinforcing fibers such as glass fibers, carbon fibers, and cellulose fibers are blended with polyolefin resins are known in order to enhance their mechanical properties. Among these fiber-reinforced resins, fiber-reinforced resins containing cellulose fibers (polyolefin resin / cellulose composite composition) have attracted attention because they are derived from biomass, are environmentally friendly, and are relatively inexpensive. As a polyolefin resin / cellulose composite composition, for example, a resin composition containing polypropylene and cellulose fibers has been proposed (Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, since the polyolefin resin / cellulose composite composition has a very high melt viscosity, its fluidity during melting is low, and many of them are inferior in molding processability. Further, in order to increase the fluidity during melting of the composite composition, even when a conventional lubricant is used, the fluidity during melting is still insufficient, and the mechanical properties may further deteriorate.

[0005] The object of the present invention is to provide a polyolefin resin / cellulose composite composition that suppresses the deterioration of mechanical properties and has good moldability.

[0006] Furthermore, an object of the present invention is to provide a novel modifier that can suppress the deterioration of the mechanical properties of a polyolefin resin / cellulose composite composition and improve the moldability of the composite composition. [Means for solving the problem]

[0007] As a result of diligent research, the inventors have found that the above problems can be solved by a resin composition comprising a predetermined polyolefin resin, predetermined celluloses, predetermined acid-modified polyolefins, and a rosin-based resin having a specific acid value and weight-average molecular weight. Furthermore, the inventors have found that the above problems can be solved by a modifier comprising a rosin-based resin having a specific acid value and weight-average molecular weight.

[0008] This disclosure provides the following items:

[0009] (Item 1) A resin composition comprising polyolefin resin (A) (however, component (C) is not included), cellulose (B), acid-modified polyolefin resin (C), and rosin-based resin (D), The acid value of the rosin-based resin (D) is 130-320 mgKOH / g. A resin composition in which the weight-average molecular weight (Mw) of the rosin-based resin (D) is 350 to 2,000.

[0010] (Item 2) The resin composition according to item 1, wherein component (D) is at least one selected from the group consisting of polymerized rosin, acrylic acid-modified rosin, fumaric acid-modified rosin, and α,β-unsaturated carboxylic acid-modified rosin ester.

[0011] (Item 3) The acid value is 130-320 mgKOH / g. The weight-average molecular weight (Mw) is between 350 and 2,000. Contains rosin-based resin (D), Modifier for polyolefin resin / cellulose composite compositions.

[0012] (Item 4) The modifier according to item 3, wherein component (D) is at least one selected from the group consisting of polymerized rosin, acrylic acid-modified rosin, fumaric acid-modified rosin, and α,β-unsaturated carboxylic acid-modified rosin esters.

[0013] (Item 5) Use of rosin-based resin (D) as a modifier for polyolefin resin / cellulose composite compositions, as described in item 1.

[0014] (Item 6) Use of the rosin-based resin (D) described in item 1 for the production of a polyolefin resin / cellulose composite composition.

[0015] In this disclosure, one or more of the features described above may be provided in combinations other than those explicitly stated. [Effects of the Invention]

[0016] The resin composition provided in this disclosure exhibits suppressed degradation of mechanical properties and good moldability. Furthermore, the modifier provided in this disclosure can improve the fluidity during melting and thus the moldability when used in a polyolefin resin / cellulose composite composition. Moreover, the modifier can suppress the degradation of mechanical properties even when used in a polyolefin resin / cellulose composite composition. [Best Mode for Carrying Out the Invention]

[0017] Throughout the present disclosure, the ranges of numerical values such as each physical property value and content can be set as appropriate (for example, selected from the values described in each of the following items). Specifically, when examples of the numerical value α are A3, A2, A1 (assuming A3 > A2 > A1), the range of the numerical value α can be, for example, A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less, etc. In the present disclosure, "~" is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value. Hereinafter, the components, manufacturing methods, etc. of the present disclosure will be described in detail.

[0018] As long as the problems of the present invention are solved, each component, condition, numerical value, etc. are not particularly limited.

[0019] "Non-volatile content" means the total mass of components other than organic solvents and water. In one embodiment, the "non-volatile content of A" means the total mass of the components remaining when 1 g of A is heated at 105°C until a constant weight is reached.

[0020] "(Meth)acryl" means "acryl and / or methacryl". "(Meth)acrylate" means "acrylate and / or methacrylate". "(Meth)acryloyl" means "acryloyl and / or methacryloyl". "(Meth)allyl" means "allyl and / or methallyl".

[0021] "Poly(meth)acrylate" means a compound having two or more (meth)acryloyl groups.

[0022] [Resin Composition] This disclosure relates to a resin composition (hereinafter simply referred to as "resin composition") comprising a polyolefin resin (A) (hereinafter also referred to as component (A)), cellulose (B) (hereinafter also referred to as component (B)), acid-modified polyolefin resin (C) (hereinafter also referred to as component (C)), and rosin-based resin (D) (hereinafter also referred to as component (D)).

[0023] <Polyolefin resin (A)> Component (A) is not particularly limited as long as it is a polyolefin resin, and various known types can be used. Component (A) may be used alone or in combination of two or more types. Note that component (A) does not contain component (C) described below.

[0024] Component (A) includes, for example, homopolymers of α-olefins having approximately 2 to 8 carbon atoms, such as ethylene, propylene, and 1-butene; binary or ternary (co)polymers of the α-olefins; and binary or ternary (co)polymers of the α-olefins with α-olefins having approximately 9 to 18 carbon atoms, conjugated dienes, unconjugated dienes, (meth)acrylic acid esters, and vinyl acetate, etc.

[0025] Examples of the above α-olefins having approximately 2 to 18 carbon atoms include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, and 1-octadecene. Examples of the above conjugated and unconjugated dienes include butadiene, isoprene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene. Examples of the above (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, and isooctyl (meth)acrylate. Two or more of these α-olefins, conjugated dienes, unconjugated dienes, and (meth)acrylic acid esters may be used.

[0026] (A) Examples of component (A) include polyethylene resins, which are polyolefin resins containing ethylene as a polymerization component, and polypropylene resins, which are polyolefin resins containing propylene as a polymerization component.

[0027] Examples of the polyethylene resins mentioned above include polyethylene such as low-density polyethylene, medium-density polyethylene, and high-density polyethylene, as well as ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-heptene copolymer, and ethylene-1-octene copolymer.

[0028] Examples of the polypropylene resins mentioned above include polypropylene, propylene-ethylene copolymer, 1-butene-propylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-4-methyl-1-pentene copolymer, and propylene-ethylene-1-hexene copolymer.

[0029] In one embodiment, component (A) preferably includes at least one selected from the group consisting of polyethylene resins and polypropylene resins, from the viewpoint of excellent mechanical properties and moldability of the resin composition.

[0030] (Physical properties of polyolefin resin (A)) The physical properties of component (A) are not particularly limited. The melt flow rate (MFR) of component (A) at a temperature of 230°C and a load of 2.16 kg is, for example, 100 g / 10 min, 95 g / 10 min, 90 g / 10 min, 85 g / 10 min, 80 g / 10 min, 75 g / 10 min, 70 g / 10 min, 69 g / 10 min, 68 g / 10 min, 67 g / 10 min, 66 g / 10 min, 65 g / 10 min, 64 g / 10 min, 63 g / 10 min, 62 g / 10 min, 61 g / 10 min, 60 g / 10 min, 59 g / 10 min, 58 g / 10 min, 57 g / 10 min, 56 g / 10 min, 55 g / 10 min, 54 g / 10 min, 53 g / 10 Examples include min, 52g / 10min, 51g / 10min, 50g / 10min, 49g / 10min, 48g / 10min, 47g / 10min, 46g / 10min, 45g / 10min, 44g / 10min, 43g / 10min, 42g / 10min, 41g / 10min, 40g / 10min, 35g / 10min, 30g / 10min, 25g / 10min, 20g / 10min, 15g / 10min, 10g / 10min, 9g / 10min, 8g / 10min, 7g / 10min, 6g / 10min, 5g / 10min, 4g / 10min, 3g / 10min, 2g / 10min, 1g / 10min, etc. In one embodiment, the melt flow rate (MFR) of component (A) at a temperature of 230°C and a load of 2.16 kg is preferably about 1 to 100 g / 10 min, and more preferably about 10 to 65 g / 10 min. The melt flow rate (MFR) of component (A) is a value measured in accordance with JIS K7210-1:2014.

[0031] <Celluloses (B)> (B) Component is not particularly limited as long as it is a type of cellulose, and various known types can be used. (B) Component may be used alone or two or more types may be used in combination.

[0032] (B) Component may include, for example, cellulose derived from raw cellulose such as natural cellulose and regenerated cellulose (hereinafter also simply referred to as raw cellulose).

[0033] Examples of the above-mentioned natural cellulose include wood pulp obtained from wood species (e.g., hardwoods or softwoods); non-wood pulp obtained from non-wood species (e.g., cotton, bamboo, hemp, bagasse, kenaf, cotton linters, sisal, straw, etc.); and cellulose fiber aggregates produced by animals (e.g., sea squirts), algae, and microorganisms (e.g., acetic acid bacteria).

[0034] Examples of the above-mentioned wood pulps include unbleached softwood kraft pulp (NUKP), bleached softwood kraft pulp (NBKP), unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), unbleached softwood sulfite pulp (NUSP), bleached softwood sulfite pulp (NBSP), thermomechanical pulp (TMP), crushed wood pulp (GP), refiner ground pulp (RGP), and chemothermetic pulp (CTMP).

[0035] Examples of the regenerated cellulose mentioned above include regenerated cellulose fibers (viscose, cupro, Tencel, etc.), cellulose derivative fibers, regenerated cellulose obtained by electrospinning, ultrafine threads of cellulose derivatives, recycled pulp, and recycled paper.

[0036] (B) The form of component (B) is not particularly limited. Examples of component (B) include fibrous, powdery, fibrous mass (cotton-like), nanofiber (cellulose nanofiber), etc.

[0037] In one embodiment, the form of component (B) is preferably fibrous, powdery, or nanofibery, from the viewpoint of excellent mechanical properties of the resin composition.

[0038] In one embodiment, component (B) or the raw material cellulose may be chemically modified or amorphous, as long as the effects of the present disclosure are not impaired.

[0039] In this disclosure, chemical modification means that the sugar chains constituting the surface of component (B) or the raw material cellulose and / or the hydroxyl groups of lignin contained in component (B) or the raw material cellulose are esterified, half-esterified (monoesterified with carboxylic acid anhydride), or etherified with an alkyl group which may have substituents, with an inorganic acid, organic acid, or carboxylic acid chloride. Furthermore, the above chemical modification also means oxidation of the primary hydroxyl groups of cellulose by TEMPO oxidation.

[0040] Examples of the esterification or half-esterification described above include esterification with acidic substances such as inorganic acids like nitric acid, sulfuric acid, phosphoric acid, and silicic acid; organic acids like acetic acid, butyric acid, and vegetable fatty acids; acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, decanoic anhydride, benzoic anhydride, and stearic anhydride; and polybasic acid anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride, alkyl or alkenyl succinic anhydrides, maleic anhydride-modified polyolefins, and maleic anhydride-modified polybutadiene.

[0041] Examples of ethers formed by the above etherification include methyl ether, hydroxyethyl ether, hydroxypropyl ether, hydroxybutyl ether, carboxymethyl ether, and cyanoethyl ether.

[0042] Amorphized component (B) or the raw material cellulose may be obtained by reducing the degree of crystallinity of component (B) or the raw material cellulose using various known methods.

[0043] In one embodiment, component (B) preferably includes cellulose derived from natural cellulose, from the viewpoint of excellent mechanical properties and moldability of the resin composition.

[0044] (Physical properties of cellulose (B)) The physical properties of component (B) are not particularly limited. The fiber lengths of component (B) are, for example, 2,000 μm, 1,950 μm, 1,900 μm, 1,850 μm, 1,800 μm, 1,750 μm, 1,700 μm, 1,650 μm, 1,600 μm, 1,550 μm, 1,500 μm, 1,450 μm, 1,400 μm, 1,350 μm, 1,300 μm, 1,250 μm, 1,200 μm, and 1,150 μm. m, 1,100μm, 1,050μm, 1,000μm, 950μm, 900μm, 850μm, 800μm, 750μm, 700μm, 650μm, 600μm, 550μm , 500μm, 450μm, 400μm, 350μm, 300μm, 250μm, 200μm, 150μm, 100μm, 95μm, 90μm, 85μm, 80μm, 75μm , 70μm, 65μm, 60μm, 55μm, 50μm, 45μm, 40μm, 35μm, 30μm, 25μm, 20μm, 15μm, 10μm, 9μm, 8μm, 7μm, 6μm, 5μm, 4μm, 3μm, 2μm, 1μm, 950nm, 900nm, 850nm, 800nm, 750nm, 700nm, 650nm, 600nm, 550nm, 5 Examples include 00nm, 450nm, 400nm, 350nm, 300nm, 250nm, 200nm, 150nm, 100nm, 95nm, 90nm, 85nm, 80nm, 75nm, 70nm, 65nm, 60nm, 55nm, 50nm, 45nm, 40nm, 35nm, 30nm, 25nm, 20nm, 15nm, 10nm, 5nm, and 1nm. In one embodiment, the fiber length of component (B) is preferably 1nm to 2,000μm, more preferably 5μm to 1,000μm, and more preferably 10μm to 900μm, from the viewpoint of excellent mechanical properties and moldability of the resin composition.

[0045] <Acid-modified polyolefin resin (C)> Component (C) is not particularly limited as long as it is a polyolefin resin having an acid group in its molecule, and various known types can be used. Component (C) may be used alone or two or more types may be used in combination.

[0046] Component (C) can improve the mechanical properties of the resin composition by improving the affinity between component (A) and component (B). Furthermore, component (C) can improve the moldability of the resin composition by increasing its fluidity during melting.

[0047] Component (C) may include, for example, a polyolefin resin that does not have acid groups, modified with a compound that has a carbon-carbon double bond (hereinafter also referred to as a C=C bond) and an acid group in its molecule.

[0048] The compounds having a C=C bond and an acid group in the above molecule are not particularly limited. One compound may be used alone, or two or more may be used in combination.

[0049] Examples of compounds having a C=C bond and an acid group in the molecule include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, unsaturated sulfonic acids, and their salts (alkali metal salts, ammonium salts, amine salts, etc.).

[0050] Examples of the above-mentioned unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, cyclohexenecarboxylic acid, cycloheptenecarboxylic acid, bicycloheptenecarboxylic acid, methyltetrahexenecarboxylic acid, and 4-vinylbenzoic acid.

[0051] Examples of the above-mentioned unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexenedicarboxylic acid, cycloheptenedicarboxylic acid, bicycloheptenedicarboxylic acid, methyltetrahydrophthalic acid, and 4,4'-stilbenedicarboxylic acid.

[0052] Examples of the above-mentioned unsaturated dicarboxylic acid anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride.

[0053] Examples of the unsaturated sulfonic acids mentioned above include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, tetradecene sulfonic acid, alkyl (C1-23) allyl sulfosuccinate, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, and dodecenebenzene sulfonic acid.

[0054] In one embodiment, the compound having a C=C bond and an acid group in the molecule is preferably at least one selected from the group consisting of the unsaturated dicarboxylic acid, the unsaturated dicarboxylic acid anhydride, and their salts, from the viewpoint of excellent mechanical properties and moldability of the resin composition, more preferably at least one selected from the group consisting of maleic acid, maleic anhydride, and salts of maleic acid, and even more preferably maleic anhydride.

[0055] The polyolefin resins that do not have the above-mentioned acid groups are not particularly limited. One type of polyolefin resin may be used alone, or two or more types may be used in combination.

[0056] Examples of polyolefin resins that do not have the above-mentioned acid groups include component (A).

[0057] The method for producing component (C) is not particularly limited as long as it involves modifying a polyolefin resin that does not have the above-mentioned acid group with a compound that has a C=C bond and an acid group in its molecule, and various known methods can be used. Specifically, examples include: a method of radical polymerization of a polyolefin resin that does not have a C=C bond in its molecule with a compound that has a C=C bond and an acid group in its molecule in the presence of a radical initiator; a method of radical polymerization of a polyolefin resin that has a C=C bond in its molecule with a compound that has a C=C bond and an acid group in its molecule in the presence of a radical initiator; a method of addition reaction of a polyolefin resin that has a C=C bond in its molecule with a compound that has a C=C bond and an acid group in its molecule in the presence or absence of a radical initiator in the presence or absence of a radical initiator of 0.3% by weight or less; and so on.

[0058] (C) Examples of polyolefin resins having C=C bonds in the molecule in the method for producing component (C) include polyolefin resins polymerized using dienes (conjugated dienes, unconjugated dienes) as monomers; and polyolefin resins obtained by a method of thermal depolymerization of polyolefin resins without C=C bonds in the molecule under nitrogen ventilation, in the absence of organic peroxides, at a temperature of 300°C to 450°C for 0.5 to 10 hours, continuously or discontinuously.

[0059] (C) The radical initiator in the method for producing component is not particularly limited. Examples of radical initiators include benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, dicumyl peroxide, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, di-t-butylperoxyhexahydroterephthalate and diallyl peroxydicarbonate, azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobiscyclohexane-1-carbonnitrile, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide). One radical initiator may be used alone, or two or more may be used in combination.

[0060] (Physical properties of acid-modified polyolefin resin (C)) The physical properties of component (C) are not particularly limited.

[0061] Examples of acid values ​​for component (C) include 60 mg KOH / g, 55 mg KOH / g, 50 mg KOH / g, 45 mg KOH / g, 40 mg KOH / g, 35 mg KOH / g, 30 mg KOH / g, 25 mg KOH / g, 20 mg KOH / g, 15 mg KOH / g, 10 mg KOH / g, 9 mg KOH / g, 8 mg KOH / g, 7 mg KOH / g, 6 mg KOH / g, 5 mg KOH / g, 4 mg KOH / g, 3 mg KOH / g, 2 mg KOH / g, 1 mg KOH / g, etc. In one embodiment, the acid value of component (C) is preferably 1 to 60 mg KOH / g, and more preferably 3 to 55 mg KOH / g, from the viewpoint of excellent mechanical properties and moldability of the resin composition. In this disclosure, the acid value of component (C) means the value measured by the following steps (1) to (3).

[0062] (1) Dissolve 1 g of component (C) as a sample in 100 g of xylene heated to 100°C. (2) Titrate with 0.1 mol / L potassium hydroxide ethanol solution using phenolphthalein as an indicator. (3) The acid value is calculated using the following formula. Acid value (mgKOH / g)=(A×f×0.1) / S However, A: the number of mL of 0.1 mol / L potassium hydroxide aqueous solution required for titration, f: Titer of 0.1 mol / L potassium hydroxide aqueous solution, S: Sample amount (g) Furthermore, the above measurement yielded results indicating that one acid anhydride group is equivalent to one carboxyl group.

[0063] Examples of weight-average molecular weights (Mw) of component (C) include 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, and 3,000. In one embodiment, the weight-average molecular weight (Mw) of component (C) is preferably 3,000 to 500,000, and more preferably 3,000 to 100,000, from the viewpoint of excellent mechanical properties and moldability of the resin composition. In this disclosure, the weight-average molecular weight (Mw) of component (C) means the value obtained by gel permeation chromatography (GPC) under the following conditions.

[0064] Equipment: High-temperature gel permeation chromatography ["Alliance GPC V2000", manufactured by Waters Co., Ltd.] Solvent: Orthodichlorobenzene Reference material: Polystyrene Sample concentration: 3 mg / ml Column stationary phase: Two PLgel 10μm MIXED-B [Polymer Laboratories, Inc.] columns connected in series. Column temperature: 135℃

[0065] <Rosin-based resin (D)> Component (D) is not particularly limited as long as its acid value and weight-average molecular weight (Mw) are within the ranges described below, and various known components can be used. Component (D) may be used alone or two or more may be used in combination.

[0066] Component (D), having an acid value and weight-average molecular weight (Mw) within the ranges described below, can increase the fluidity during melting in the resin composition and improve moldability. Furthermore, component (D), having an acid value and weight-average molecular weight (Mw) within the ranges described below, can suppress the deterioration of the mechanical properties in the resin composition.

[0067] Component (D) includes, for example, polymerized rosin, α,β-unsaturated carboxylic acid modified rosin, α,β-unsaturated carboxylic acid modified rosin ester, etc.

[0068] (Polymerized rosin) The polymerized rosin described above is not particularly limited. The polymerized rosin can be obtained by various known means. Specifically, the polymerized rosin can be obtained, for example, by reacting (polymerizing) natural rosin or purified rosin (hereinafter, natural rosin and purified rosin are collectively referred to as unmodified rosin) as a raw material in the presence of a catalyst and, if necessary, an organic solvent.

[0069] The natural rosin mentioned above includes, for example, natural rosin (gum rosin, tall oil rosin, wood rosin) derived from species such as Pinus massoniana, Pinus elliottii, Pinus yunnanensis, Pinus merkusii, Pinus caribaea, Pinus tropicalis, Pinus kesiya, Pinus taeda, Pinus palustris, Pinus sylvestris var. mongolica, Pinus resinosa, Pinus strobus, and Pinus halepensis.

[0070] The purified rosin described above can be obtained using various known methods. Specifically, purified rosin can be obtained using various known purification methods such as distillation, extraction, recrystallization, and adsorption. Distillation methods include, for example, distilling the natural rosin at a temperature of approximately 200-300°C and under reduced pressure of approximately 0.01-3 kPa. Extraction methods include, for example, making an alkaline aqueous solution of the natural rosin, extracting the insoluble unsaponifiable matter with various organic solvents, and then neutralizing the aqueous layer. Recrystallization methods include, for example, dissolving the natural rosin in an organic solvent as a good solvent, then distilling off the solvent to obtain a concentrated solution, and then adding an organic solvent as a poor solvent. Good solvents include, for example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; chlorinated hydrocarbon solvents such as chloroform; lower alcohols; ketones such as acetone; and acetic acid esters such as ethyl acetate. Poor solvents include, for example, n-hexane, n-heptane, cyclohexane, and isooctane. Adsorption methods include, for example, contacting a porous adsorbent with the above-mentioned natural rosin in a molten state or in a solution form dissolved in an organic solvent. Examples of porous adsorbents include activated carbon, metal oxides such as alumina, zirconia, silica, molecular sieves, zeolites, and porous clay with micropores.

[0071] The catalyst used in the production of polymerized rosin can be any known catalyst. Examples of such catalysts include sulfuric acid, formic acid, acetic acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, solid acids having sulfonic acid groups, polymers having pendant sulfonic acid groups such as polystyrene sulfonic acid, polyvinyl sulfonic acid, or fluorinated polymers having sulfonic acid-type functional groups, hydrogen fluoride, zinc chloride, aluminum chloride, titanium tetrachloride, boron trifluoride, and boron trifluoride derivatives such as boron trifluoride phenol complex, boron trifluoride dimethyl ether complex, or boron trifluoride diethyl ether complex. One catalyst may be used alone, or two or more may be used in combination. In one embodiment, the catalyst is preferably at least one selected from the group consisting of sulfuric acid, formic acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, solid acids having sulfonic acid groups, and zinc chloride, from the viewpoint of ease of catalyst removal after the reaction. In one embodiment, the amount of catalyst used is preferably about 0.1 to 90 parts by weight per 100 parts by weight of rosin ester, and more preferably about 1 to 20 parts by weight in order to suppress side reactions.

[0072] The organic solvent used in the polymerization reaction is not particularly limited and can be any known solvent, as long as it does not inhibit the polymerization reaction of unmodified rosin. Examples of such organic solvents include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as heptane and octane; ketone hydrocarbons such as methyl ethyl ketone and methyl isopropyl ketone; ester hydrocarbons such as ethyl acetate and butyl acetate; halogenated hydrocarbons such as carbon tetrachloride, ethylene dichloride, trichloroethane, and tetratrichloroethane; acetic acid, propionic acid, butyric acid, and their anhydrides; carboxyl group-containing organic acids such as formic acid, chloroacetic acid, and lactic acid. One organic solvent may be used alone, or two or more may be used in combination. In one embodiment, the organic solvent is preferably aromatic hydrocarbons and aliphatic hydrocarbons, and more preferably xylene, heptane, or octane, as these facilitate the recovery and reuse of the organic solvent after the reaction. The amount of organic solvent used is not particularly limited. In one embodiment, the amount of organic solvent used is preferably about 5 to 900 parts by weight, and more preferably about 10 to 500 parts by weight, per 100 parts by weight of unmodified rosin.

[0073] The above reaction (polymerization) conditions are not particularly limited. Examples of reaction (polymerization) conditions include a method of reacting at a temperature of about 0 to 200°C, preferably 40 to 200°C, for about 0.5 to 24 hours. In one embodiment, after the reaction (polymerization) is completed, the above organic solvent used, the above catalyst, unreacted unmodified rosin, and decomposition products may be removed from the polymerized product as needed. Examples of methods for removing the above catalyst include washing with water, alkali neutralization, and filtration. Examples of methods for removing unreacted unmodified rosin and decomposition products include vacuum distillation. In one embodiment, the distillation conditions for vacuum distillation are preferably a temperature of 200 to 290°C and a vacuum of 60 to 8000 Pa.

[0074] Specific examples of the polymerized rosins mentioned above include gum polymerized rosins using gum rosin as a raw material (for example, product name "Polymerized Rosin B-140," manufactured by Xinzhou (Wuping) Forestry Co., Ltd.), tall oil polymerized rosins using tall oil rosin (for example, product name "Silvatac 140," manufactured by Arizona Chemical Co., Ltd.), and wood polymerized rosins using wood rosin (for example, product name "Dymarex," manufactured by Eastman Chemical Co., Ltd.).

[0075] In one embodiment, the polymerized rosin may be obtained by subjecting the polymerized rosin to the above-mentioned purification, hydrogenation, disproportionation, and various treatments such as α,β-unsaturated carboxylic acid modification, including acrylication, maleation, and fumaration, as described later. Furthermore, these various treatments may be performed individually or in combination of two or more.

[0076] The above disproportionation can be achieved, for example, by heating various rosins in the presence of a disproportionation catalyst. As the disproportionation catalyst, various known supported catalysts such as palladium-carbon, rhodium-carbon, and platinum-carbon; metal powders such as nickel and platinum; and various known iodides such as iodine and iron iodide can be used. In one embodiment, the amount of catalyst used is usually about 0.01 to 5 parts by mass, preferably about 0.01 to 1 part by mass, per 100 parts by mass of various rosins. In one embodiment, the reaction temperature is about 100 to 300°C, preferably about 150 to 290°C.

[0077] The above hydrogenation can be described, for example, by using known hydrogenation conditions to hydrogenate various rosins. Examples of hydrogenation conditions include heating various rosins to a temperature of 100 to 300°C at a hydrogen pressure of about 2 to 20 MPa in the presence of a hydrogenation catalyst. In one embodiment, the hydrogen pressure is preferably about 5 to 20 MPa. In one embodiment, the reaction temperature is preferably about 150 to 300°C. Various known hydrogenation catalysts can be used, such as supported catalysts and metal powders. Examples of supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, and platinum-carbon. Examples of metal powders include nickel and platinum. In one embodiment, the metal powder is preferably a palladium, rhodium, ruthenium, and platinum-based catalyst. In one embodiment, by using these as metal powders, the hydrogenation rate of various rosins is increased and the hydrogenation time is shortened. In one embodiment, the amount of hydrogenation catalyst used is typically about 0.01 to 5 parts by mass, preferably about 0.01 to 2 parts by mass, per 100 parts by mass of various rosins.

[0078] In one embodiment, the hydrogenation may be carried out with various rosins dissolved in a solvent as needed. The solvent used is not particularly limited. In one embodiment, the solvent is preferably one that is inert to the reaction and in which the raw materials and products are easily dissolved. Specifically, the solvent can be one or more of the following: cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane, etc. In one embodiment, the amount of solvent used is usually such that the non-volatile content is 10% by mass or more relative to the various rosins, and preferably such that the non-volatile content is about 10 to 70% by mass.

[0079] (α,β-unsaturated carboxylic acid-modified rosin) The above-mentioned α,β-unsaturated carboxylic acid-modified rosin is obtained by adding an α,β-unsaturated carboxylic acid to the above-mentioned unmodified rosin.

[0080] The above α,β-unsaturated carboxylic acid is not particularly limited, and various known ones can be used. Specifically, examples of α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, muconic anhydride, maleic acid half ester, fumaric acid half ester, itaconic acid half ester, and so on. In one embodiment, the above α,β-unsaturated carboxylic acid is preferably acrylic acid, maleic acid, maleic anhydride, or fumaric acid. In one embodiment, the amount of α,β-unsaturated carboxylic acid used is usually about 1 to 20 parts by mass, preferably about 1 to 3 parts by mass, per 100 parts by mass of the above unmodified rosin, from the viewpoint of excellent fluidity when melted and excellent moldability.

[0081] The above α,β-unsaturated carboxylic acid-modified rosin can be obtained by various known means. Specifically, the α,β-unsaturated carboxylic acid-modified rosin can be obtained, for example, by adding the above α,β-unsaturated carboxylic acid to the above unmodified rosin melted under heating, and reacting it at a temperature of about 180 to 240°C for about 1 to 9 hours. In one embodiment, the above reaction may be carried out while blowing an inert gas such as nitrogen into a sealed reaction system. In one embodiment, the above reaction may be carried out using a known catalyst such as a Lewis acid such as zinc chloride, iron chloride, or tin chloride, or a Brønsted acid such as p-toluenesulfonic acid or methanesulfonic acid. In one embodiment, the amount of these catalysts used is usually about 0.01 to 10% by mass relative to the above unmodified rosin.

[0082] In one embodiment, the α,β-unsaturated carboxylic acid-modified rosin may be obtained by further subjecting the α,β-unsaturated carboxylic acid-modified rosin to the above-mentioned purification, hydrogenation, disproportionation, and other treatments. Furthermore, these treatments may be performed individually or in combination of two or more.

[0083] (α,β-unsaturated carboxylic acid modified rosin ester) The above-mentioned α,β-unsaturated carboxylic acid-modified rosin ester is a reaction product of the above-mentioned α,β-unsaturated carboxylic acid-modified rosin and alcohol.

[0084] The above alcohols are not particularly limited and various known alcohols can be used. Examples of the above alcohols include monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, cyclohexanol, benzyl alcohol, borneol, etc.; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, etc. Examples include dihydric alcohols such as chlorohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-isopropylidenedicyclohexanol, and 4,8-bis(hydroxymethyl)tricyclo[5.2.1.02,6]decane; trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane; tetrahydric alcohols such as pentaerythritol, diglycerin, and di(trimethylolpropane); pentahydric alcohols such as triglycerin; and hexahydric alcohols such as dipentaerythritol. Note that glycidyl ethers or glycidol, which react with carboxylic acids to form esters, may also be used. The above alcohols may be used individually or in combination of two or more.

[0085] In one embodiment, the alcohol is preferably a 3- to 6-hydric alcohol, and more preferably glycerin, pentaerythritol, diglycerin, or dipentaerythritol.

[0086] The above-mentioned α,β-unsaturated carboxylic acid-modified rosin ester can be obtained by various known means. Specifically, the above-mentioned α,β-unsaturated carboxylic acid-modified rosin ester can be obtained, for example, by reacting the above-mentioned α,β-unsaturated carboxylic acid-modified rosin with the above-mentioned alcohol at a temperature of about 150 to 300°C for about 1 to 24 hours. The amounts of the above-mentioned α,β-unsaturated carboxylic acid-modified rosin and alcohol used are not particularly limited. In one embodiment, the amounts of the above-mentioned α,β-unsaturated carboxylic acid-modified rosin and alcohol used are usually determined so that the ratio of OH groups of alcohol to COOH groups of α,β-unsaturated carboxylic acid-modified rosin (equivalent ratio) is in the range of about 0.8 to 8, preferably about 1.1 to 1.3.

[0087] In one embodiment, in the method for producing the α,β-unsaturated carboxylic acid-modified rosin ester described above, the esterification reaction may be carried out in the presence of a catalyst in order to shorten the reaction time. Examples of catalysts include acid catalysts such as p-toluenesulfonic acid, acetic acid, methanesulfonic acid, hypophosphorous acid, and sulfuric acid; metal hydroxides such as calcium hydroxide and magnesium hydroxide; metal oxides such as calcium oxide and magnesium oxide; and metal salts such as iron chloride and calcium formate. One type of catalyst may be used alone, or two or more types may be used in combination. Also, water is produced as a result of the esterification reaction. Therefore, the reaction can be carried out while removing the produced water from the system. In one embodiment, considering the color tone of the obtained α,β-unsaturated carboxylic acid-modified rosin ester, it is preferable to carry out the reaction under an inert gas stream. In one embodiment, the reaction may be carried out under pressure if necessary.

[0088] In one embodiment, the method for producing the α,β-unsaturated carboxylic acid-modified rosin esters described above may involve reacting the α,β-unsaturated carboxylic acid-modified rosin with an organic solvent that is nonreactive to the alcohol. Examples of such organic solvents include hexane, cyclohexane, toluene, and xylene. When an organic solvent is used, the organic solvent or unreacted raw materials may be removed by vacuum distillation as needed.

[0089] In one embodiment, the method for producing the α,β-unsaturated carboxylic acid-modified rosin ester described above may involve further treatment of the obtained α,β-unsaturated carboxylic acid-modified rosin ester, such as purification, hydrogenation, disproportionation, and α,β-unsaturated carboxylic acid modification. Furthermore, these treatments may be performed individually or in combination of two or more.

[0090] In one embodiment, the method for producing the α,β-unsaturated carboxylic acid-modified rosin ester may be a method of carrying out a modification reaction with an α,β-unsaturated carboxylic acid on the reaction product of the unmodified rosin and the alcohol.

[0091] In one embodiment, component (D) is preferably at least one selected from the group consisting of polymerized rosin, α,β-unsaturated carboxylic acid modified rosin, and α,β-unsaturated carboxylic acid modified rosin ester, from the viewpoint of superior mechanical properties and moldability of the resin composition. More preferably, from the viewpoint of similarity, at least one selected from the group consisting of polymerized rosin, acrylic acid modified rosin, fumaric acid modified rosin, and α,β-unsaturated carboxylic acid modified rosin ester, and more preferably, polymerized rosin.

[0092] In one embodiment, component (D) may optionally include various known additives, provided that they do not impair the effects of the present disclosure. Examples of additives include dehydrating agents, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, and light stabilizers. These additives may be used individually or in combination of two or more.

[0093] Examples of the above-mentioned antioxidants include phenol sulfides, thiophosphites, phosphorus compounds, hindered phenols, and xanthones.

[0094] The content of the above additive is not particularly limited. Examples of the content of the above additive include 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., per 100 parts by mass of component (D). In one embodiment, the content of the above additive is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (D).

[0095] (Physical properties of rosin-based resin (D)) (D) The acid value (mgKOH / g) of component is, for example, 320mgKOH / g, 315mgKOH / g, 310mgKOH / g, 305mgKOH / g, 300mgKOH / g, 295mgKOH / g, 290mgKOH / g, 285mgKOH / g, 280mgKOH / g, 275mgKOH / g, 270mgKOH / g, 265mgKOH / g, 260mgKOH / g, 255mgKOH / g, 250 mgKOH / g, 245mgKOH / g, 240mgKOH / g, 235mgKOH / g, 230mgKOH / g, 225mgKOH / g, 220mgKOH / g, 215mgKOH / g, 210mg KOH / g, 205mgKOH / g, 200mgKOH / g, 195mgKOH / g, 190mgKOH / g, 185mgKOH / g, 180mgKOH / g, 175mgKOH / g, 170mgKOH / g, 169mgKOH / g, 168mgKOH / g, 167mgKOH / g, 166mgKOH / g, 165mgKOH / g, 164mgKOH / g, 163mgKOH / g, 162mgKOH / g , 161mgKOH / g, 160mgKOH / g, 159mgKOH / g, 158mgKOH / g, 157mgKOH / g, 156mgKOH / g, 155mgKOH / g, 154mgKOH / g, 15 Examples include 3 mg KOH / g, 152 mg KOH / g, 151 mg KOH / g, 150 mg KOH / g, 149 mg KOH / g, 148 mg KOH / g, 147 mg KOH / g, 146 mg KOH / g, 145 mg KOH / g, 144 mg KOH / g, 143 mg KOH / g, 142 mg KOH / g, 141 mg KOH / g, 140 mg KOH / g, 135 mg KOH / g, 130 mg KOH / g, etc. In one embodiment, the acid value of component (D) is preferably 130 mg KOH / g or more, from the viewpoint of excellent mechanical properties and moldability of the resin composition. In one embodiment, the acid value of component (D) is preferably 320 mg KOH / g or less, and more preferably 310 mg KOH / g or less, from the viewpoint of excellent mechanical properties and moldability of the resin composition. In one embodiment, the acid value of component (D) is preferably about 130 to 320 mgKOH / g, and more preferably about 130 to 310 mgKOH / g, from the viewpoint of excellent mechanical properties and moldability of the resin composition.In this disclosure, the acid value is the value measured according to JIS K0070.

[0096] If the acid value of component (D) is less than 130 mgKOH / g, the moldability of the resin composition tends to be poor. Examples of such rosin-based resins include rosin esters, which are reaction products of alcohol with rosin acid (e.g., natural rosin, purified rosin, hydrogenated rosin, disproportionated rosin), which are rosin-based resins having a carboxyl group in the molecule other than polymerized rosin and α,β-unsaturated carboxylic acid modified rosin. If the acid value of component (D) is greater than 320 mgKOH / g, the mechanical properties of the resin composition tend to be poor.

[0097] Examples of weight-average molecular weights (Mw) of component (D) include 2,000, 1,900, 1,800, 1,700, 1,600, 1,500, 1,400, 1,300, 1,200, 1,100, 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 490, 480, 470, 460, 450, 440, 430, 420, 410, 400, 390, 380, 370, 360, and 350. In one embodiment, the weight-average molecular weight of component (D) is preferably 350 or higher, from the viewpoint of excellent mechanical properties and moldability of the resin composition. In one embodiment, the weight-average molecular weight of component (D) is preferably 2,000 or less, and more preferably 600 or less, from the viewpoint of excellent mechanical properties and moldability of the resin composition. In one embodiment, the weight-average molecular weight of component (D) is preferably about 350 to 2,000, and more preferably about 350 to 600, from the viewpoint of excellent mechanical properties and moldability of the resin composition. In this disclosure, the weight-average molecular weight is the polystyrene equivalent value obtained by gel permeation chromatography (GPC).

[0098] (D) When the weight-average molecular weight (Mw) of component is less than 350, the moldability of the resin composition tends to be poor. Examples of such rosin-based resins include rosin acids (e.g., natural rosin, purified rosin, hydrogenated rosin, disproportionated rosin) and diterpene-type resin acids (e.g., abietic acid, pimaric acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, dihydroagatoic acid, combunic acid), which are rosin-based resins having a carboxyl group in the molecule other than polymerized rosin and α,β-unsaturated carboxylic acid-modified rosin.

[0099] (D) The physical properties of component (D) are not particularly limited to those other than the acid value and weight-average molecular weight mentioned above.

[0100] In one embodiment, component (D) may optionally include various known additives, provided that they do not impair the effects of the present invention. Examples of additives include dehydrating agents, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, and light stabilizers. These additives may be used individually or in combination of two or more.

[0101] (Additives) In one embodiment, the resin composition may optionally contain additives, provided that they do not impair the effects of the present disclosure. Examples of additives include flame retardants, conductivity imparters, nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insecticides, deodorants, color inhibitors, heat stabilizers, mold release agents, antistatic agents, plasticizers, colorants, dyes, foaming agents, antifoaming agents, coupling agents, inorganic pigments, organic pigments, fluidity improvers other than component (D), light stabilizers, and the like.

[0102] Furthermore, it is undesirable for the above resin composition to contain polyamines. When polyamines are included in the above resin composition, the moldability of the resin composition tends to decrease. Examples of such polyamines include aliphatic polyamines and aromatic polyamines. Examples of such aliphatic polyamines include polyethyleneimine and polyalkyleneimines such as polytrimethyleneimine.

[0103] (Content of each component) The content of component (A) in the above resin composition is not particularly limited. Examples of the content of component (A) in the above resin composition include 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, and 15 parts by mass, per 100 parts by mass of the resin composition. In one embodiment, the content of component (A) in the above resin composition is preferably about 15 to 90 parts by mass, and more preferably about 35 to 80 parts by mass, per 100 parts by mass of the resin composition, from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0104] The content of component (A) in the above resin composition can be, for example, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, etc., based on 100 parts by mass of the total of components (A) and (B). In one embodiment, the content of component (A) in the above resin composition is preferably about 20 to 90 parts by mass, and more preferably about 40 to 80 parts by mass, based on 100 parts by mass of the total of components (A) and (B), from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0105] The content of component (B) in the above resin composition is not particularly limited. Examples of the content of component (B) in the above resin composition include 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, 10 parts by mass, and 5 parts by mass, per 100 parts by mass of the resin composition. In one embodiment, the content of component (B) in the above resin composition is preferably about 5 to 80 parts by mass, and more preferably about 15 to 60 parts by mass, per 100 parts by mass of the resin composition, from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0106] The content of component (B) in the above resin composition can be, for example, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, or 10 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). In one embodiment, the content of component (B) in the above resin composition is preferably about 10 to 80 parts by mass, and more preferably about 20 to 60 parts by mass, relative to 100 parts by mass of the total of components (A) and (B), from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0107] Examples of the content ratio ((A) / (B)) of component (A) and component (B) in the above resin composition include 90 / 10, 85 / 15, 80 / 20, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, etc. In one embodiment, the content ratio ((A) / (B)) of component (A) and component (B) in the above resin composition is preferably around 20 / 80 to 90 / 10, and more preferably around 40 / 60 to 80 / 20, from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0108] The content of component (C) in the above resin composition is not particularly limited. Examples of the content of component (C) in the above resin composition include 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, 0.09 parts by mass, 0.08 parts by mass, 0.07 parts by mass, 0.06 parts by mass, 0.05 parts by mass, etc., per 100 parts by mass of the resin composition. In one embodiment, the content of component (C) in the above resin composition is preferably about 0.05 to 10 parts by mass, and more preferably about 0.2 to 8 parts by mass, from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0109] The content of component (C) in the above resin composition can be, for example, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., relative to 100 parts by mass of the total of components (A) and (B). In one embodiment, the content of component (C) in the above resin composition is preferably about 0.1 to 8 parts by mass, and more preferably about 0.3 to 5 parts by mass, relative to 100 parts by mass of the total of components (A) and (B), from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0110] The content of component (D) in the above resin composition is not particularly limited. Examples of the content of component (D) in the above resin composition include 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., per 100 parts by mass of the resin composition. In one embodiment, the content of component (D) in the above resin composition is preferably about 0.1 to 13 parts by mass, and more preferably about 0.5 to 8 parts by mass, from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0111] The content of component (D) in the above resin composition can be, for example, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., relative to 100 parts by mass of the total of components (A) and (B). In one embodiment, the content of component (D) in the above resin composition is preferably about 0.1 to 15 parts by mass, more preferably about 0.3 to 10 parts by mass, and even more preferably about 0.3 to 5 parts by mass, relative to 100 parts by mass of the total of components (A) and (B), from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0112] The content of component (D) in the above resin composition can be, for example, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., relative to 100 parts by mass of the total of components (A) and (D). In one embodiment, the content of component (D) in the above resin composition is preferably about 0.1 to 14 parts by mass, and more preferably about 0.4 to 11 parts by mass, relative to 100 parts by mass of the total of components (A) and (D), from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0113] If the content of component (D) in the above resin composition is less than 0.1 parts by mass per 100 parts by mass of the total of components (A) and (D), the resin composition tends to have poor moldability. If the content of component (D) in the above resin composition is more than 14 parts by mass per 100 parts by mass of the total of components (A) and (D), the resin composition tends to have poor mechanical properties.

[0114] The content of component (C) in the above resin composition can be, for example, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., relative to 100 parts by mass of the total of components (A), (C), and (D). In one embodiment, the content of component (C) in the above resin composition is preferably about 0.1 to 11 parts by mass, and more preferably about 0.6 to 7 parts by mass, relative to 100 parts by mass of the total of components (A), (C), and (D), from the viewpoint of superior mechanical properties and moldability of the resin composition.

[0115] If the content of component (C) in the above resin composition is less than 0.1 parts by mass per 100 parts by mass of the total of components (A), (C), and (D), the mechanical properties of the resin composition tend to be inferior. If the content of component (C) in the above resin composition is more than 11 parts by mass per 100 parts by mass of the total of components (A), (C), and (D), the moldability of the resin composition tends to be inferior.

[0116] The content of the additive in the above resin composition is not particularly limited. Examples of the content of the additive in the above resin composition include 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, 10 parts by mass, 5 parts by mass, 1 part by mass, 0.5 parts by mass, 0.1 parts by mass, 0.05 parts by mass, 0.01 parts by mass, 0.005 parts by mass, 0.001 parts by mass, etc., per 100 parts by mass of the above resin composition. In one embodiment, the content of the additive in the above resin composition is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more, per 100 parts by mass of the above resin composition. In one embodiment, the content of the additive in the resin composition is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less, per 100 parts by mass of the resin composition.

[0117] (Method for manufacturing resin compositions) The method for producing the above resin composition is not particularly limited, and various known methods can be employed. For example, one method for producing the above resin composition is to pre-mix components (A), (B), (C), and (D), and optionally the above additives, using various mixers such as a tumbler mixer or a Henschel mixer, and then melt-knead the mixture using a mixer such as a Banbury mixer, roll mixer, brabender, single-screw extruder, twin-screw extruder, or kneader. The temperature of the melt-kneading is not particularly limited, but is usually in the range of -30°C to +30°C, which is the melting point of the thermoplastic resin.

[0118] In the production of the above resin composition, using component (D) increases the fluidity of the resin composition during melt-kneading, resulting in excellent productivity.

[0119] [Molded body] The molded articles of this disclosure are obtained by molding the above-mentioned resin composition by various known molding methods. There are no particular restrictions on the shape of the molded article, and it can be appropriately selected according to the application and purpose of the molded article. Examples include plate-shaped, rod-shaped, sheet-shaped, film-shaped, cylindrical, annular, circular, elliptical, polygonal, irregularly shaped, hollow, frame-shaped, box-shaped, and panel-shaped articles.

[0120] The method for forming the above-mentioned molded article is not particularly limited, and conventionally known molding methods can be employed. Specifically, examples include injection molding, injection compression molding, extrusion molding, stretch film molding, inflation molding, shape extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating) molding, press molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding. Among these, molding is preferably carried out by injection molding. Examples of injection molding machines include known injection molding machines such as ultra-high-speed injection molding machines and injection compression molding machines.

[0121] The above-mentioned molded products can be used for a variety of applications, including automotive parts, home appliances, electrical and electronic components, building materials, various containers, daily necessities, household goods, and hygiene products.

[0122] [Modifier for polyolefin resin / cellulose composite compositions] This disclosure relates to a modifier (hereinafter also referred to as "modifier") for polyolefin resin / cellulose composite compositions, comprising the above-described component (D).

[0123] The above-mentioned modifier, when used in a polyolefin resin / cellulose composite composition, functions to improve its fluidity during melting (as a fluidity enhancer). Furthermore, when used in a polyolefin resin / cellulose composite composition, the above-mentioned modifier can suppress the deterioration of its mechanical properties.

[0124] In one embodiment, component (D) in the modifier is preferably at least one selected from the group consisting of polymerized rosin, acrylic acid-modified rosin, fumaric acid-modified rosin, and α,β-unsaturated carboxylic acid-modified rosin ester, from the viewpoint of further improving the mechanical properties and moldability of the polyolefin resin / cellulose composite composition, and polymerized rosin is more preferred from the same viewpoint.

[0125] The acid value (mgKOH / g) of component (D) in the above modifier is, for example, 320mgKOH / g, 315mgKOH / g, 310mgKOH / g, 305mgKOH / g, 300mgKOH / g, 295mgKOH / g, 290mgKOH / g, 285mgKOH / g, 280mgKOH / g, 275mgKOH / g, 270mgKOH / g, 265mgKOH / g, 260mgKOH / g, 255mgKOH / g, 250mgKOH / g, 245mgKOH / g, 240mgKOH / g, 235mgKOH / g, 230mgKOH / g, 225mgKOH / g, 220mgKOH / g, 215mgKOH / g, 210mgKOH / g, 205mgKOH / g, 200mgKOH / g, 195mgKOH / g, 190mgKOH / g, 185mgKOH / g, 180mgKOH / g, 175mgKOH / g, 170m gKOH / g, 169mgKOH / g, 168mgKOH / g, 167mgKOH / g, 166mgKOH / g, 165mgKOH / g, 164mgKOH / g, 163mgKOH / g, 162mgKO H / g, 161mgKOH / g, 160mgKOH / g, 159mgKOH / g, 158mgKOH / g, 157mgKOH / g, 156mgKOH / g, 155mgKOH / g, 154mgKOH / g, Examples include 153 mg KOH / g, 152 mg KOH / g, 151 mg KOH / g, 150 mg KOH / g, 149 mg KOH / g, 148 mg KOH / g, 147 mg KOH / g, 146 mg KOH / g, 145 mg KOH / g, 144 mg KOH / g, 143 mg KOH / g, 142 mg KOH / g, 141 mg KOH / g, 140 mg KOH / g, 135 mg KOH / g, 130 mg KOH / g, etc. In one embodiment, the acid value of component (D) in the modifier is preferably 130 mg KOH / g or higher, from the viewpoint of further improving the mechanical properties and moldability of the polyolefin resin / cellulose composite composition. In one embodiment, the acid value of component (D) in the modifier is preferably 320 mg KOH / g or less, and more preferably 310 mg KOH / g or less, from the viewpoint of further improving the mechanical properties and moldability of the polyolefin resin / cellulose composite composition.In one embodiment, the acid value of component (D) in the modifier is preferably about 130 to 320 mgKOH / g, and more preferably about 130 to 310 mgKOH / g, from the viewpoint of further improving the mechanical properties and moldability of the polyolefin resin / cellulose composite composition. In this disclosure, the acid value is the value measured according to JIS K0070.

[0126] When the acid value of component (D) in the above modifier is less than 130 mgKOH / g, the moldability of the polyolefin resin / cellulose composite composition tends to decrease. Examples of such rosin-based resins include rosin esters, which are reaction products of alcohol with rosin acid (e.g., natural rosin, purified rosin, hydrogenated rosin, disproportionated rosin), which are rosin-based resins having a carboxyl group in the molecule other than polymerized rosin and α,β-unsaturated carboxylic acid modified rosin. When the acid value of component (D) in the above modifier is greater than 320 mgKOH / g, the mechanical properties of the polyolefin resin / cellulose composite composition tend to decrease.

[0127] Examples of weight-average molecular weights (Mw) of component (D) in the above-mentioned modifier include 2,000, 1,900, 1,800, 1,700, 1,600, 1,500, 1,400, 1,300, 1,200, 1,100, 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 490, 480, 470, 460, 450, 440, 430, 420, 410, 400, 390, 380, 370, 360, and 350. In one embodiment, the weight-average molecular weight of component (D) in the above-mentioned modifier is preferably 350 or higher, from the viewpoint of further improving the mechanical properties and moldability of the polyolefin resin / cellulose composite composition. In one embodiment, the weight-average molecular weight of component (D) in the modifier is preferably 2,000 or less, and more preferably 600 or less, from the viewpoint of further improving the mechanical properties and moldability of the polyolefin resin / cellulose composite composition. In one embodiment, the weight-average molecular weight of component (D) in the modifier is preferably about 350 to 2,000, and more preferably about 350 to 600, from the viewpoint of further improving the mechanical properties and moldability of the polyolefin resin / cellulose composite composition. In this disclosure, the weight-average molecular weight is the polystyrene equivalent value obtained by gel permeation chromatography (GPC).

[0128] When the weight-average molecular weight (Mw) of component (D) in the above modifier is less than 350, the moldability of the polyolefin resin / cellulose composite composition tends to decrease. Examples of such rosin-based resins include rosin acids other than polymerized rosin and α,β-unsaturated carboxylic acid-modified rosin (e.g., natural rosin, purified rosin, hydrogenated rosin, disproportionated rosin), and diterpene-type resin acids (e.g., abietic acid, pimaric acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, dihydroagatoic acid, combunic acid).

[0129] The physical properties of component (D) in the above-mentioned modifier are not particularly limited to those of the above-mentioned acid value and weight-average molecular weight.

[0130] (Additives) In one embodiment, the modifier may optionally include various known additives, as long as the effects of the present invention are not impaired. Examples of additives include dehydrating agents, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, and light stabilizers. The additives may be used individually or in combination of two or more. In one embodiment, the content of the additive is preferably 0.5 to 10 parts by mass per 100 parts by mass of the rosin-based resin.

[0131] (Use of modifiers for polyolefin resin / cellulose composite compositions) The above modifier can be used with various known polyolefin resin / cellulose composite compositions. Examples of the above polyolefin resin / cellulose composite compositions include compositions containing a polyolefin resin and cellulose. Examples of the polyolefin resin include component (A) above. The polyolefin resin may be used alone or in combination of two or more types. Examples of the above cellulose include component (B) above. The cellulose may be used alone or in combination of two or more types.

[0132] In one embodiment, the polyolefin resin in the polyolefin resin / cellulose composite composition preferably includes at least one selected from the group consisting of polyethylene resins and polypropylene resins, from the viewpoint of excellent mechanical properties and moldability of the polyolefin resin / cellulose composite composition.

[0133] In one embodiment, the cellulose in the polyolefin resin / cellulose composite composition preferably includes cellulose derived from natural cellulose, in order to provide excellent mechanical properties and moldability of the polyolefin resin / cellulose composite composition.

[0134] In one embodiment, the polyolefin resin / cellulose composite composition using the modifier may optionally contain an acid-modified polyolefin resin, provided that the effects of the present disclosure are not impaired. The acid-modified polyolefin resin, when used in the polyolefin resin / cellulose composite composition, can improve the affinity between the polyolefin resin and cellulose, thereby improving the mechanical properties of the polyolefin resin / cellulose composite composition. Furthermore, the acid-modified polyolefin resin can improve the moldability of the polyolefin resin / cellulose composite composition by increasing its fluidity during melting.

[0135] The above-mentioned acid-modified polyolefin resin may include, for example, component (C) described above. The above-mentioned acid-modified polyolefin resin may be used alone or in combination of two or more types. Note that the above-mentioned polyolefin resin does not contain the above-mentioned acid-modified polyolefin resin.

[0136] In one embodiment, the polyolefin resin / cellulose composite composition using the modifier may optionally contain additives, provided that they do not impair the effects of the present disclosure. Examples of additives include those described above in the resin composition.

[0137] The content of the polyolefin resin, cellulose, acid-modified polyolefin resin, and additives in the above polyolefin resin / cellulose composite composition is not particularly limited. Examples of the content of the polyolefin resin, cellulose, acid-modified polyolefin resin, and additives include the content of component (A), component (B), component (C), and additives in the above resin composition.

[0138] The amount of the modifier used is not particularly limited. Examples of the amount of the modifier used include 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., per 100 parts by mass of the polyolefin resin / cellulose composite composition. In one embodiment, the amount of the modifier used is preferably about 0.1 to 13 parts by mass, more preferably about 0.5 to 8 parts by mass, per 100 parts by mass of the polyolefin resin / cellulose composite composition, in order to improve the moldability of the polyolefin resin / cellulose composite composition and suppress the decrease in the mechanical properties of the composite composition.

[0139] The amount of the above-mentioned modifier used is, for example, 15 parts by mass, 14 parts by mass, 13 parts by mass, 12 parts by mass, 11 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, 7 parts by mass, 6 parts by mass, 5 parts by mass, 4 parts by mass, 3 parts by mass, 2 parts by mass, 1 part by mass, 0.9 parts by mass, 0.8 parts by mass, 0.7 parts by mass, 0.6 parts by mass, 0.5 parts by mass, 0.4 parts by mass, 0.3 parts by mass, 0.2 parts by mass, 0.1 parts by mass, etc., per 100 parts by mass of the total of the polyolefin resin and cellulose. In one embodiment, the amount of the above-mentioned modifier used is preferably about 0.1 to 15 parts by mass, more preferably about 0.3 to 10 parts by mass, and even more preferably about 0.3 to 5 parts by mass, per 100 parts by mass of the total of the polyolefin resin and cellulose, in order to improve the moldability of the polyolefin resin / cellulose composite composition and suppress the decrease in the mechanical properties of the composite composition.

[0140] The method of using the above-mentioned modifier is not particularly limited. For example, one method of using the above-mentioned modifier is to add the above-mentioned polyolefin resin and cellulose, and optionally the above-mentioned acid-modified polyolefin resin and additives, to a mixer and then melt-knead the mixture in the mixer. Examples of the above-mentioned mixer include a Banbury mixer, roll mixer, Brabender, single-screw extruder, twin-screw extruder, kneader, etc. The temperature of the melt-kneading is not particularly limited, but is usually in the range of -30°C to +30°C, which is the melting point of the thermoplastic resin.

[0141] [Use as a modifier for polyolefin resin / cellulose composite compositions] The above-mentioned component (D) can be used as a modifier for polyolefin resin / cellulose composite compositions. When component (D) is used in a polyolefin resin / cellulose composite composition, it functions to improve its fluidity during melting (fluidity enhancer) and also suppresses the deterioration of the mechanical properties of the composite composition. The polyolefin resin / cellulose composite composition is not particularly limited, and examples include those described above.

[0142] In one embodiment, component (D) is preferably used as a modifier for a polyolefin resin / cellulose composite composition containing a polyolefin resin and cellulose, which includes at least one selected from the group consisting of polyethylene resins and polypropylene resins, in order to further improve the fluidity of the polyolefin resin / cellulose composite composition when it melts and to further suppress the deterioration of its mechanical properties.

[0143] In one embodiment, component (D) is preferably used as a modifier for a polyolefin resin / cellulose composite composition containing cellulose derived from natural cellulose and a polyolefin resin, as it further improves the fluidity of the polyolefin resin / cellulose composite composition when melted and further suppresses the deterioration of its mechanical properties.

[0144] In one embodiment, component (D) is preferably used as a modifier in a polyolefin resin / cellulose composite composition that includes an acid-modified polyolefin resin, as it further improves the fluidity of the polyolefin resin / cellulose composite composition during melting and further suppresses the deterioration of its mechanical properties. The acid-modified polyolefin resin is not particularly limited and includes, for example, those described above.

[0145] The amount of component (D) used as a modifier in the polyolefin resin / cellulose composite composition is not particularly limited. Examples of the amount of component (D) used include the amount of the modifier described above. [Examples]

[0146] The present invention will be described in more detail below with reference to examples of the present invention, but the present invention is actually... This is not limited to the examples provided. Note that "part" and "%" in the examples refer to, respectively... This represents "parts by mass" and "mass %".

[0147] <Manufacturing of rosin-based resins> Manufacturing Example 1 In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and vacuum device, 700 parts of Chinese gum rosin (acid value 170.0 mg KOH / g, softening point 78°C, color 6 Gardner), 700 parts of xylene, and 17.5 parts of zinc chloride as a catalyst were charged, and the polymerization reaction was carried out at 140°C for 2 hours under a nitrogen stream. After filtering off the catalyst from the reaction product, xylene was removed by distillation under conditions of a liquid temperature of less than 200°C and a vacuum of 1300 Pa. Then, rosin decomposition products and unreacted gum rosin were further removed by distillation under conditions of a liquid temperature of 200-275°C and a vacuum of 400 Pa to obtain polymerized rosin (hereinafter referred to as component (D1)).

[0148] Manufacturing Example 2 In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and vacuum device, 700 parts of Chinese gum rosin (acid value 170.0 mg KOH / g, softening point 78°C, color 6 Gardner), 700 parts of xylene, and 17.5 parts of zinc chloride as a catalyst were charged, and the polymerization reaction was carried out at 140°C for 1 hour under a nitrogen stream. After filtering off the catalyst from the reaction product, xylene was removed by distillation under conditions of a liquid temperature of less than 200°C and a vacuum of 1300 Pa. Then, rosin decomposition products and unreacted gum rosin were further removed by distillation under conditions of a liquid temperature of 200-275°C and a vacuum of 400 Pa to obtain polymerized rosin (hereinafter referred to as component (D2)).

[0149] Manufacturing Example 3 In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and vacuum device, 700 parts of Chinese gum rosin (acid value 170.0 mg KOH / g, softening point 78°C, color 6 Gardner), 700 parts of xylene, and 17.5 parts of zinc chloride as a catalyst were charged, and the polymerization reaction was carried out at 140°C for 7 hours under a nitrogen stream. After filtering off the catalyst from the reaction product, xylene was removed by distillation under conditions of a liquid temperature of less than 200°C and a vacuum of 1300 Pa. Then, rosin decomposition products and unreacted gum rosin were further removed by distillation under conditions of a liquid temperature of 200-275°C and a vacuum of 400 Pa to obtain polymerized rosin (hereinafter referred to as component (D3)).

[0150] Manufacturing Example 4 In a reaction vessel equipped with a stirrer, reflux condenser with water divider, and thermometer, 1,000 parts of Chinese gum rosin were charged and heated to 180°C under a nitrogen atmosphere while stirring until melted. Then, 267 parts of fumaric acid were added, and the temperature was raised to 230°C while stirring, and the temperature was maintained for 1 hour to obtain fumaric acid-modified rosin (hereinafter referred to as component (D4)).

[0151] Manufacturing Example 5 1000 parts of Chinese gum rosin (acid value 172 mg KOH / g, softening point 75°C, color 6 Gardner) and 500 parts of xylene were placed in a corvene and heated until dissolved. Approximately 350 parts of xylene were removed by distillation, then 350 parts of cyclohexane were added, and the mixture was cooled to room temperature. When approximately 100 parts of crystals formed due to cooling, the supernatant was transferred to another corvene and recrystallized at room temperature. After removing the supernatant, the mixture was washed with 100 parts of cyclohexane, and the solvent was removed by distillation to obtain 700 parts of purified rosin.

[0152] Next, 660 parts of purified rosin and 100 parts of acrylic acid were charged into a reaction vessel, and the reaction was carried out at 220°C for 4 hours while stirring under a nitrogen atmosphere. Then, unreacted material was removed under reduced pressure to obtain 720 parts of the addition reaction product.

[0153] Furthermore, 500 parts of the above addition reaction product and 5.0 parts of 5% palladium carbon (50% water content) were placed in a 1-liter rotary autoclave. After removing oxygen from the system, the system was pressurized with hydrogen to 10 MPa and heated to 220°C. A hydrogenation reaction was carried out at the same temperature for 3 hours to obtain the hydride of acrylic acid-modified rosin (hereinafter referred to as component (D5)).

[0154] Manufacturing Example 6 Chinese gum rosin (acid value 172 mgKOH / g, softening point 75°C, color 6 Gardner) was charged into a vacuum distillation vessel and distilled under reduced pressure of 0.4 kPa under a nitrogen seal to obtain purified rosin with an acid value of 177 mgKOH / g, softening point 80°C, and color 3 Gardner.

[0155] Next, 700 parts of the purified rosin and 140 parts of maleic anhydride were charged into another vacuum distillation vessel and reacted at 220°C for 4 hours while stirring under a nitrogen stream. After that, unreacted material was removed under reduced pressure of 4 kPa to obtain the addition reaction product.

[0156] Furthermore, 500 parts of the addition reaction product and 6.0 parts of 5% palladium carbon (50% water content) (catalyst amount 1.2%) were placed in a 1-liter rotary autoclave. After replacing the air in the system with hydrogen, the autoclave was pressurized to 10 MPa with hydrogen, the temperature was raised to 220°C, and the hydrogenation reaction was carried out at the same temperature for 5 hours. The catalyst was filtered off to obtain a hydride of maleic anhydride-modified rosin (hereinafter referred to as component (D6)).

[0157] Comparative Manufacturing Example 1 In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and vacuum device, 500 parts of Chinese gum rosin and 60 parts of glycerin were charged. The mixture was heated to 270°C under a nitrogen atmosphere and reacted at the same temperature for 12 hours. After that, the pressure was reduced to 8 kPa and the reaction was continued for 2 hours to obtain rosin glycerin ester (hereinafter referred to as component (D1')).

[0158] Comparative Manufacturing Example 2 In a reaction vessel equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and steam inlet tube, 100 parts of Chinese gum rosin and 8.5 parts of maleic anhydride were charged. The mixture was then reacted at 220°C for 2 hours under a nitrogen gas stream. After that, 18 parts of pentaerythritol and 2 parts of glycerin were charged, and the temperature was raised to 275°C, where the reaction was continued for 14 hours to complete the esterification. Subsequently, the reaction vessel was depressurized to remove moisture and other contaminants, yielding maleic acid-modified rosin ester.

[0159] Next, 80 parts of the obtained maleic acid-modified rosin ester and 20 parts of component (D4) were charged and mixed at 200°C for 1 hour to obtain a mixed resin of maleic acid-modified rosin ester and fumaric acid-modified rosin (hereinafter referred to as component (D2')).

[0160] (Measurement of weight-average molecular weight (Mw)) The weight-average molecular weight (Mw) of components (D1) to (D6), components (D1') to (D2'), and CG-WW (described later) was calculated as a polystyrene equivalent value obtained from a calibration curve of standard polystyrene using gel permeation chromatography (GPC). The GPC method was measured under the following conditions. The results are shown in Table 1. Analytical instrument: HLC-8320 (manufactured by Tosoh Corporation) Columns: TSK guardcolumn HH, TSK-GEL SUPER HM-L x 3 columns connected together Eluent: Tetrahydrofuran Injection sample concentration: 5 mg / mL Flow rate: 0.6mL / min Injection volume: 40μL Column temperature: 40℃ Detector: RI, UV (254nm)

[0161] (Measurement of acid value) The acid values ​​of components (D1) to (D6), components (D1') to (D2'), and CG-WW (described later) were measured according to JIS K 0070. The results are shown in Table 1.

[0162] [Table 1]

[0163] [Preparation of resin compositions and molded articles] Example 1 70 parts of polypropylene (manufactured by Sun Allomer Co., Ltd., product name "PMB60A") (hereinafter referred to as component (A1)), 30 parts of cellulose fiber (manufactured by Rettenmeyer, product name "Arbocell BC1000") (hereinafter referred to as component (B1)), 1 part of acid-modified polypropylene (manufactured by Sanyo Chemical Industries, Ltd., product name "Yumex 1010") (hereinafter referred to as component (C1)), and 0.5 parts of component (D1) were added to a roller mixer type kneading device (manufactured by Toyo Seiki Mfg. Co., Ltd., product name "Labo Plastmill Model 10C100"), 30 parts of cellulose fiber (manufactured by Rettenmeyer, product name "Arbocell BC1000") (hereinafter referred to as component (B1)), 1 part of acid-modified polypropylene (manufactured by Sanyo Chemical Industries, Ltd., product name "Yumex 1010") (hereinafter referred to as component (C1)), and 0.5 parts of component (D1). The mixture was kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 190°C to obtain a kneaded material (resin composition). Subsequently, the obtained kneaded material was removed from the kneading device, hot-pressed at 200°C to form a sheet with a thickness of 1.0 mm, and then cut into 5 mm x 5 mm pieces using a cutting machine to obtain pellets.

[0164] Examples 2-3 In Example 1, the preparation was carried out in the same manner as in Example 1, except that component (D1) was replaced with components (D2) to (D3), to obtain a resin composition and pellets.

[0165] Examples 4-6 The resin composition and pellets were prepared in the same manner as in Example 1, except that component (D1) was replaced with a portion of components (D4) to (D6).

[0166] Example 7 The preparation was carried out in the same manner as in Example 1, except that component (D1) was replaced with 15 parts of component (D3), to obtain a resin composition and pellets.

[0167] Comparative Example 1 The preparation was carried out in the same manner as in Example 1, except that component (D1) was not used, to obtain a resin composition and pellets.

[0168] Comparative Example 2 The preparation was carried out in the same manner as in Example 1, except that component (C1) was not used, to obtain a resin composition and pellets.

[0169] Comparative Example 3 In Example 1, the preparation was carried out in the same manner as in Example 1, except that component (D1) was changed to component (D1'), to obtain a resin composition and pellets.

[0170] Comparative Example 4 In Example 1, the preparation was carried out in the same manner as in Example 1, except that component (D1) was replaced with component (D2'), to obtain a resin composition and pellets.

[0171] Comparative Example 5 In Example 1, the preparation was carried out in the same manner as in Example 1, except that component (D1) was replaced with Chinese gum rosin (hereinafter referred to as CG-WW), to obtain a resin composition and pellets.

[0172] Comparative Example 6 70 parts of component (A1), 30 parts of component (B1), 1 part of component (C1), 0.5 parts of component (D2), and 0.4 parts of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., product name "Epomin SP-003") were added to a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Laboplastmill Model 10C100"), and the mixture was kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 190°C to obtain a kneaded product (resin composition). The obtained kneaded product was then removed from the kneading device, hot-pressed at 200°C to form a sheet with a thickness of 1.0 mm, and cut into 5 mm x 5 mm pieces using a cutting machine to obtain pellets.

[0173] Comparative Example 7 The preparation was carried out in the same manner as in Example 1, except that components (C1) and (D1) were not used, to obtain a resin composition and pellets.

[0174] (MFR evaluation) In accordance with JIS K 7210, the MFR of each pellet from Examples 1-7 and Comparative Examples 1-7 was measured under conditions of a temperature of 190°C and a load of 49.0 N (5.0 kg). The results are shown in Table 2. A higher MFR value indicates better moldability.

[0175] (Evaluation of bending stress) The resin compositions of Examples 1-7 and Comparative Examples 1-7 were injection molded using a hand truder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a resin melting temperature of 200°C and a mold temperature of 50°C to create rectangular test specimens (length 80 mm x width 10 mm x thickness 4 mm). The bending stress (MPa) of the prepared rectangular test specimens was measured using a Tensilon universal testing machine (product name "RTG-1250", manufactured by A&D Co., Ltd.) in accordance with JIS K7171, with a support distance of 64 mm, a test speed of 2 mm / min, a temperature of 23°C, and a 50% RH environment. The results are shown in Table 2. A higher bending stress (MPa) indicates better mechanical properties.

[0176] [Table 2]

Claims

1. The resin composition comprises polyolefin resin (A) (however, component (C) is not included), cellulose (B), acid-modified polyolefin resin (C), and rosin-based resin (D). The acid value of the rosin-based resin (D) is 130 to 320 mgKOH / g. A resin composition wherein the weight-average molecular weight (Mw) of the rosin-based resin (D) is 350 to 2,000.

2. The resin composition according to claim 1, wherein component (D) is at least one selected from the group consisting of polymerized rosin, acrylic acid-modified rosin, fumaric acid-modified rosin, and α,β-unsaturated carboxylic acid-modified rosin ester.

3. The acid value is 130-320 mgKOH / g. The weight-average molecular weight (Mw) is between 350 and 2,000. Contains rosin-based resin (D), Modifier for polyolefin resin / cellulose composite compositions.

4. The modifier according to claim 3, wherein component (D) is at least one selected from the group consisting of polymerized rosin, acrylic acid-modified rosin, fumaric acid-modified rosin, and α,β-unsaturated carboxylic acid-modified rosin ester.

5. Use of the rosin-based resin (D) according to claim 1 as a modifier for use in polyolefin resin / cellulose composite compositions.

6. Use of the rosin-based resin (D) according to claim 1 for producing a polyolefin resin / cellulose composite composition.

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