WO2024095883A1

WO2024095883A1 - Modifier for thermoplastic resin, resin composition, and use of rosin resin

Info

Publication number: WO2024095883A1
Application number: PCT/JP2023/038658
Authority: WO
Inventors: 翼伊藤; 昭寛川端; 功基柴地; 徹也柏原; 遼芝原; 隆中谷
Original assignee: 荒川化学工業株式会社
Priority date: 2022-11-01
Filing date: 2023-10-26
Publication date: 2024-05-10

Abstract

A modifier for a thermoplastic resin that contains a rosin resin having a mass residual rate after heating for two hours at 300°C of 40 mass% or more and a mixed methylcyclohexane aniline cloud point (MMAP) of from -10 to 20°C.

Description

Use of modifier for thermoplastic resin, resin composition and rosin-based resin

The present invention relates to the use of a modifier for thermoplastic resins, a resin composition, and a rosin-based resin.

Thermoplastic resins are used in a variety of industrial fields, and among them, engineering plastics and super engineering plastics are widely used as automotive materials, electrical and electronic equipment materials, and housing and building materials due to their excellent balance of heat resistance and strength. However, the above-mentioned thermoplastic resins, particularly engineering plastics and super engineering plastics, often have high molding temperatures and poor melt fluidity, so additives such as lubricants are usually added to the thermoplastic resin to reduce the apparent flow viscosity during melting and improve molding processability (Patent Documents 1 and 2).

JP 2012-009754 A JP 2004-137423 A

However, even when conventional lubricants are used, some thermoplastic resins still have insufficient fluidity when melted, resulting in poor moldability. Furthermore, thermoplastic resins, particularly engineering plastics and super engineering plastics, have high melting points of approximately 200°C or higher, and are melted at high temperatures (250°C or higher). However, the addition of conventional lubricants can cause smoke during melting.

The present invention aims to provide a novel modifier for thermoplastic resins that can suppress smoke generation during melting of the thermoplastic resin and improve the molding processability of the thermoplastic resin.

After extensive research, the inventors discovered that the above problems could be solved by using a modifier for thermoplastic resins that contains a rosin-based resin that has a high mass retention rate after heating at 300°C for two hours and has a specific mixed methylcyclohexaneaniline cloud point (MMAP).

The present invention has been made to solve at least some of the problems described above, and can be realized in the following aspects or application examples.

(Item 1)
The mass residual rate after heating at 300° C. for 2 hours is 40% by mass or more,
The rosin-based resin has a mixed methylcyclohexaneaniline cloud point (MMAP) of -10 to 20°C.
Modifier for thermoplastic resins.

(Item 2)
A resin composition comprising the modifier according to item 1 and a thermoplastic resin.

(Item 3)
3. The resin composition according to item 2, wherein the thermoplastic resin comprises at least one selected from the group consisting of polyamide, polycarbonate, polyphenylene ether and polyolefin resin.

(Item 4)
4. The resin composition according to item 2 or 3, further comprising a filler.

(Item 5)
5. The resin composition according to item 4, wherein the filler comprises at least one selected from the group consisting of glass fiber, carbon powder, calcium carbonate, cellulose powder and cellulose fiber.

(Item 6)
2. Use of the rosin-based resin according to claim 1 as a modifier for thermoplastic resins.

(Item 7)
7. The use according to claim 6, wherein the thermoplastic resin further comprises a filler.

(Item 8)
2. Use of the rosin-based resin according to claim 1 for producing a resin composition containing a thermoplastic resin.

(Item 9)
9. The use according to claim 8, wherein the resin composition further comprises a filler.

Throughout this disclosure, the range of the values of each physical property, content, etc. may be set as appropriate (for example, by selecting from the values described in each item below). Specifically, when the examples of the value α are A3, A2, and A1 (A3>A2>A1), the range of the value α may 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 A2, greater than A2 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 less than A3, greater than A1 and less than A2, greater than A2 and less than A3, and so on. In this disclosure, the word "to" is used to mean that the values described before and after it are included as the lower and upper limits. Below, the components and manufacturing methods of this disclosure will be described in detail.

[Modifier for thermoplastic resin]
The present disclosure relates to a modifier for thermoplastic resins (hereinafter also referred to as modifier), which contains a rosin-based resin (hereinafter also referred to as rosin-based resin) having a mass retention rate (hereinafter also referred to as mass retention rate) of 40 mass% or more after heating at 300°C for 2 hours and a mixed methylcyclohexaneaniline cloud point (MMAP) (hereinafter also referred to as MMAP) of -10 to 20°C.

When used in thermoplastic resins, the above modifiers function to improve the fluidity of the thermoplastic resin when melted (fluidity improvers).

<Rosin-based resin>
The rosin-based resin is not particularly limited as long as the mass residual rate and MMAP are within the above-mentioned ranges, and various known resins can be used. The rosin-based resins may be used alone or in combination of two or more.

The above-mentioned rosin-based resins include, for example, rosin esters, rosin polyols, etc.

(rosin esters)
The rosin esters are not particularly limited, and various known rosin esters can be used. Examples of the rosin esters include unmodified rosin esters, hydrogenated rosin esters, disproportionated rosin esters, polymerized rosin esters, and α,β-unsaturated carboxylic acid modified rosin esters. The rosin esters may be used alone or in combination of two or more.

Unmodified rosin esters are obtained by reacting natural rosin or refined rosin (hereinafter, natural rosin and refined rosin are collectively referred to as unmodified rosin) with alcohols.

The above-mentioned natural rosins include, for example, natural rosins (gum rosin, tall oil rosin, wood rosin) derived from Pinus massoniana, slash pine (Pinus elliottii), Pinus merkusii, Caribbean pine (Pinus caribaea), Pinus kesiya, Loblolly pine (Pinus taeda), and Pinus palustris.

The purified rosin can be obtained by using various known means. Specifically, it can be obtained by using various known purification means such as distillation, extraction, recrystallization, and adsorption. The distillation method includes, for example, a method of distilling the natural rosin at a temperature of about 200 to 300°C under a reduced pressure of about 0.01 to 3 kPa. The extraction method includes, for example, a method of making the natural rosin into an alkaline aqueous solution, extracting insoluble unsaponifiable matter with various organic solvents, and then neutralizing the aqueous layer. The recrystallization method includes, for example, a method of dissolving the natural rosin in an organic solvent as a good solvent, then distilling off the solvent to obtain a concentrated solution, and further adding an organic solvent as a poor solvent. Examples of good solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, chlorinated hydrocarbon solvents such as chloroform, lower alcohols, ketones such as acetone, and acetate esters such as ethyl acetate. Examples of poor solvents include n-hexane, n-heptane, cyclohexane, and isooctane. The adsorption method may, for example, be a method in which the natural rosin in a molten state or the natural rosin in a solution state dissolved in an organic solvent is brought into contact with a porous adsorbent. Examples of the porous adsorbent include activated carbon, metal oxides such as alumina, zirconia, silica, molecular sieves, zeolites, and porous clays with fine pores.

Furthermore, the purified rosin obtained may be subjected to the disproportionation and hydrogenation operations described below, either alone or in combination of two or more thereof.

In order to improve the color tone, the purified rosin may be further subjected to a dehydrogenation treatment. The dehydrogenation treatment is not particularly limited, and normal conditions can be adopted. For example, the purified rosin is dehydrogenated in a closed vessel in the presence of a dehydrogenation catalyst at an initial hydrogen pressure of less than 10 kg/cm2, preferably less than 5 kg/cm2, and at a reaction temperature of about 100 to 300°C, preferably in the range of a lower limit of 200°C and an upper limit of 280°C. There are no particular limitations on the dehydrogenation catalyst, and various known catalysts can be used, but preferred examples include palladium-, rhodium-, and platinum-based catalysts, which are usually used supported on a carrier such as silica or carbon. The amount of the catalyst used is usually about 0.01 to 5% by weight, preferably a lower limit of 0.05% by weight and an upper limit of 3% by weight, based on the purified rosin.

The alcohols are not particularly limited, and examples thereof include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimer diol, bisphenol A, and bisphenol F; trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane; tetrahydric alcohols such as pentaerythritol and diglycerin; and hexahydric alcohols such as dipentaerythritol. In one embodiment, polyhydric alcohols having three or more hydroxyl groups are preferred, in view of the high mass retention rate in the rosin-based resin, and more preferably glycerin, pentaerythritol, diglycerin, and dipentaerythritol. The alcohols may be used alone or in combination of two or more.

In one embodiment, the alcohols are preferably two or more selected from the group consisting of dihydric alcohols, trihydric alcohols, tetrahydric alcohols, and hexahydric alcohols, because they have a high mass residual rate in the rosin-based resin. In one embodiment, the dihydric alcohols are preferably bisphenol A and bisphenol F, because they have a high mass residual rate in the rosin-based resin.

The reaction conditions of the unmodified rosin and alcohols are not particularly limited, and various known reaction conditions can be used. The reaction conditions of the unmodified rosin and alcohols may be, for example, the unmodified rosin and alcohols in the presence or absence of a solvent, with an esterification catalyst added as necessary, at about 250 to 280°C for about 1 to 8 hours.

The above-mentioned esterification catalyst includes, for example, acid catalysts such as paratoluenesulfonic 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. The catalyst may be used alone or in combination of two or more. Furthermore, since water is produced as a result of the esterification reaction, the reaction can be allowed to proceed while removing the produced water from the system. Considering the color tone of the resulting unmodified rosin ester, it is desirable to carry out the reaction under an inert gas flow. Furthermore, the reaction may be carried out under pressure if necessary.

Examples of the solvent include hexane, cyclohexane, toluene, and xylene. When a solvent is used, the solvent or unreacted raw materials can be removed by distillation under reduced pressure, if necessary.

In one embodiment, the amount of the unmodified rosin and alcohols used is such that the OH group of the alcohols/COOH group of the unmodified rosins (equivalent ratio) is about 0.2 to 8, and is preferably about 0.8 to 8, and more preferably about 0.8 to 3, in view of the high mass residual rate in the rosin-based resin.

Hydrogenated rosin ester is obtained by subjecting the unmodified rosin described above to a hydrogenation reaction, and then reacting the hydrogenated rosin with alcohols to esterify it.

The hydrogenated rosin can be obtained by using various known means. Specifically, for example, the unmodified rosin can be reacted (hydrogenated) by heating under hydrogen pressure in the presence of a hydrogenation catalyst. As the hydrogenation catalyst, various known catalysts such as supported catalysts and metal powders can be used. Supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, platinum-carbon, etc., and metal powders include nickel and platinum. In one embodiment, the amount of the catalyst used is usually about 0.01 to 5 parts by mass, preferably about 0.01 to 2 parts by mass, per 100 parts by mass of the rosin used as the raw material. In one embodiment, the hydrogen pressure is about 2 to 20 MPa, preferably about 5 to 20 MPa. In one embodiment, the reaction temperature is about 100 to 300°C, preferably about 150°C to 300°C.

The hydrogenation may be carried out, if necessary, with the unmodified rosin dissolved in a solvent. There is no particular limit to the solvent used, as long as it is inert to the reaction and easily dissolves the raw materials and products. Specifically, for example, cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane, etc. can be used alone or in combination of two or more. There is no particular limit to the amount of solvent used, but it is usually sufficient to use a solvent so that the solid content is 10% by mass or more, preferably 10 to 70% by mass, relative to the unmodified rosin.

In addition, the hydrogenated rosin obtained may be subjected to the above-mentioned purification, hydrogenation, and disproportionation operations described below, either alone or in combination of two or more thereof.

In addition, in order to improve the color tone, the hydrogenated rosin may be further subjected to the above-mentioned dehydrogenation treatment.

The reaction conditions for the hydrogenated rosin and the alcohols are the same as those for the unmodified rosin ester. The alcohols used in esterifying the hydrogenated rosin are also the same as those described above. Furthermore, the amounts of the hydrogenated rosin and the alcohols used are also the same as those described above.

The order of the hydrogenation reaction and the esterification reaction is not limited to the above, and the hydrogenation reaction may be carried out after the esterification reaction.

Disproportionated rosin ester is obtained by disproportionating the unmodified rosin described above, and then reacting the resulting disproportionated rosin with alcohols to esterify it.

The disproportionated rosin can be obtained by using various known means. Specifically, for example, the unmodified rosin can be reacted (disproportionated) by heating in the presence of a disproportionation catalyst. Examples of the disproportionation catalyst include supported catalysts such as palladium-carbon, rhodium-carbon, and platinum-carbon, metal powders such as nickel and platinum, and iodides such as iodine and iron iodide. In one embodiment, the amount of the catalyst used is usually about 0.01 to 5 parts by mass, and preferably about 0.01 to 1 part by mass, per 100 parts by mass of the rosin used as the raw material. In one embodiment, the reaction temperature is about 100 to 300°C, and preferably about 150 to 290°C.

Furthermore, the disproportionated rosin obtained may be subjected to the above-mentioned purification, hydrogenation, and disproportionation operations, either alone or in combination of two or more thereof.

In addition, in order to improve the color tone, the disproportionated rosin may be subjected to the above-mentioned dehydrogenation treatment.

The reaction conditions for the disproportionated rosin and the alcohols are the same as those for the unmodified rosin ester. The alcohols used when esterifying the disproportionated rosin are also the same as those described above. Furthermore, the amounts of the disproportionated rosin and the alcohols used are also the same as those described above.

The order of the disproportionation reaction and the esterification reaction is not limited to the above, and the disproportionation reaction may be carried out after the esterification reaction.

Polymerized rosin ester is obtained by reacting polymerized rosin with alcohols. Polymerized rosin is a rosin derivative that contains dimerized resin acid.

　A publicly known method can be used to produce the polymerized rosin. Specifically, for example, the raw material is the unmodified rosin, which is reacted in a solvent such as toluene or xylene containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride, or titanium tetrachloride at a reaction temperature of about 40 to 160°C for about 1 to 5 hours.

The polymerized rosin may be obtained by subjecting the obtained polymerized rosin to various treatments, such as the above-mentioned purification, hydrogenation, disproportionation, and α,β-unsaturated carboxylic acid modification such as acrylation, maleinization, and fumaration, which will be described later. The various treatments may be performed alone or in combination of two or more.

The reaction conditions for the polymerized rosin and alcohols are the same as those for the unmodified rosin ester. The amounts of polymerized rosin and alcohols used are also the same as those described above. Furthermore, the unmodified rosin may be used in combination with the polymerized rosin, and these may be reacted with the alcohols.

The alcohols used when esterifying polymerized rosin are the same as those described above.

The order of the polymerization reaction and the esterification reaction is not limited to the above, and the polymerization reaction may be carried out after the esterification reaction.

α,β-unsaturated carboxylic acid modified rosin ester is obtained by reacting α,β-unsaturated carboxylic acid modified rosin with alcohols.

The above-mentioned α,β-unsaturated carboxylic acid modified rosin is obtained by subjecting the above-mentioned unmodified rosin, hydrogenated rosin or disproportionated rosin to an addition reaction with α,β-unsaturated carboxylic acid.

The α,β-unsaturated carboxylic acid is not particularly limited, and various known α,β-unsaturated carboxylic acids can be used. Specific examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, muconic anhydride, and the like. In one embodiment, the α,β-unsaturated carboxylic acid is preferably acrylic acid, maleic acid, maleic anhydride, or fumaric acid. In one embodiment, the amount of the α,β-unsaturated carboxylic acid used is usually about 1 to 20 parts by mass, and preferably about 1 to 3 parts by mass, per 100 parts by mass of the unmodified rosin, from the viewpoint of excellent emulsification properties. The α,β-unsaturated carboxylic acids may be used alone or in combination of two or more kinds.

The method for producing the α,β-unsaturated carboxylic acid modified rosin is not particularly limited, but may be, for example, adding the α,β-unsaturated carboxylic acid to the unmodified rosin or disproportionated rosin melted under heating, and reacting for about 1 to 9 hours at a temperature of about 180 to 240°C. The reaction may be carried out while blowing an inert gas such as nitrogen into a sealed reaction system. Furthermore, the reaction may use known catalysts such as Lewis acids such as zinc chloride, iron chloride, and tin chloride, and Bronsted acids such as paratoluenesulfonic acid and methanesulfonic acid. The amount of these catalysts used is usually about 0.01 to 10 mass% based on the unmodified rosin.

The α,β-unsaturated carboxylic acid modified rosin may be an α,β-unsaturated carboxylic acid modified rosin that has been further subjected to the above-mentioned hydrogenation.

　The reaction conditions between the α,β-unsaturated carboxylic acid modified rosin and alcohols are not particularly limited, but for example, alcohol is added to the α,β-unsaturated carboxylic acid modified rosin that has been melted under heating, and the reaction is carried out at a temperature of about 250 to 280°C for about 15 to 20 hours. The reaction may also be carried out while blowing an inert gas such as nitrogen into the sealed reaction system, and the above-mentioned catalyst may also be used.

The alcohols used when esterifying the α,β-unsaturated carboxylic acid modified rosin are the same as above. The amounts of the α,β-unsaturated carboxylic acid modified rosin and alcohols used are also the same as above.

Furthermore, as the unmodified rosin ester, the hydrogenated rosin ester, the disproportionated rosin ester, the polymerized rosin ester, and the α,β-unsaturated carboxylic acid modified rosin ester, the rosin ester obtained may be subjected to various treatments such as the purification, hydrogenation, disproportionation, and dehydrogenation treatment. Moreover, the various treatments may be used alone or in combination of two or more.

In one embodiment, the rosin ester is preferably at least one selected from the group consisting of hydrogenated rosin ester and disproportionated rosin ester, since the mass retention rate is high.

(rosin polyol)
Rosin polyols are the reaction products of reactive components that include rosins and epoxy resins.

The rosins are not particularly limited, and various known rosins can be used. Examples of the rosins include the unmodified rosin, hydrogenated rosin, and disproportionated rosin.

The epoxy resin is not particularly limited, and various known epoxy resins can be used. Examples of the epoxy resin include bisphenol type epoxy resins, novolac type epoxy resins, resorcinol type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, aliphatic polyepoxy compounds, alicyclic epoxy compounds, glycidylamine type epoxy compounds, glycidyl ester type epoxy compounds, monoepoxy compounds, naphthalene type epoxy compounds, biphenyl type epoxy compounds, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene block copolymers, epoxy group-containing polyester resins, epoxy group-containing polyurethane resins, epoxy group-containing acrylic resins, stilbene type epoxy compounds, triazine type epoxy compounds, fluorene type epoxy compounds, triphenolmethane type epoxy compounds, alkyl-modified triphenolmethane type epoxy compounds, dicyclopentadiene type epoxy compounds, aryl alkylene type epoxy compounds, trihydroxybiphenyl triglycidyl ether, 1,1,2,2-tetra(4-hydroxyphenyl)ethane tetraglycidyl ether, and the like.

The above-mentioned bisphenol type epoxy resins include, for example, bisphenol A type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, hydrogenated bisphenol AD type epoxy resins, tetrabromobisphenol A type epoxy resins, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl diglycidyl ether, 2,2-bis(4-(β-hydroxypropoxy)phenyl)propane diglycidyl ether, etc.

Examples of the novolac type epoxy resin include cresol novolac type epoxy resin, phenol novolac type epoxy resin, α-naphthol novolac type epoxy resin, bisphenol A type novolac type epoxy resin, and brominated phenol novolac type epoxy resin.

Examples of the aliphatic polyepoxy compounds include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, and diglycidyl ether.

The above alicyclic epoxy compounds include, for example, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, and the like.

Examples of the glycidylamine type epoxy compounds include tetraglycidyldiaminodiphenylmethane, triglycidyl paraaminophenol, triglycidyl metaaminophenol, and tetraglycidyl metaxylylenediamine.

Examples of the glycidyl ester type epoxy compounds include diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, triglycidyl trimellitate, etc.

The weight average molecular weight (Mw) of the epoxy resin is not particularly limited. The weight average molecular weight of the epoxy resin is, for example, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, 1,800, 1,900, 2,000, 2,100, 2,200, 2,300, 2,400, 2,500, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 11,000, 12,000, 13,000, 14,000, 15,000, 16,000, 17,000, 18,000, 19,000, 20,000, 21,000, 22,000, 23,000, 24,000, 25,000, 26,000, 27,000, 28,000, 29,000, 30,000, 31,000, 32,000, 33,000, 34,000, 35,000, 36,000, 37,000, 38,000, 39,000, 40,000, 41,000, 42,000, 43, 00, 2,600, 2,700, 2,800, 2,900, 3,000, 3,100, 3,200, 3,300, 3,400, 3,500, 3,600, 3,700, 3,800, 3,900, 4,000, 4,100, 4,200, 4,300, 4,400, 4,500, 4,600, 4,700, 4,800, 4,900, 5,000, 5,0 00, 5,100, 5,200, 5,300, 5,400, 5,500, 5,600, 5,700, 5,800, 5,900, 6,000, 6,100, 6,200, 6,300, 6,400, 6,500, 6,600, 6,700, 6,800, 6,900, 7,000, 7,100, 7,200, 7,300, 7,400, 7,500, 7, Examples of the weight average molecular weight of the epoxy resin include 600, 7,700, 7,800, 7,900, 8,000, 8,100, 8,200, 8,300, 8,400, 8,500, 8,600, 8,700, 8,800, 8,900, 9,000, 9,100, 9,200, 9,300, 9,400, 9,500, 9,600, 9,700, 9,800, 9,900, and 10,000. In one embodiment, the weight average molecular weight of the epoxy resin is preferably 150 or more because the mass residual rate in the rosin-based resin is high. The higher the weight average molecular weight of the epoxy resin, the higher the mass residual rate tends to be. In one embodiment, the weight average molecular weight of the epoxy resin is preferably about 150 to 10,000, more preferably about 150 to 2,000, in order to further improve the fluidity of the thermoplastic resin when melted. The weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

The epoxy equivalent (g/eq) of the epoxy resin is not particularly limited. The epoxy equivalent of the epoxy resin is, for example, 100 g/eq, 150 g/eq, 180 g/eq, 200 g/eq, 300 g/eq, 400 g/eq, 500 g/eq, 600 g/eq, 700 g/eq, 800 g/eq, 900 g/eq, 1,000 g/eq, 1,100 g/eq, 1, 200g/eq, 1,300g/eq, 1,400g/eq, 1,500g/eq, 1,600g/eq, 1,700g/eq, 1,800g/eq, 1,900g/eq, 2,000g/eq, 2,100g/eq, 2,200g/eq, 2,300g/eq, 2,400g/eq, 2,50 0 g/eq, 2,600 g/eq, 2,700 g/eq, 2,800 g/eq, 2,900 g/eq, 3,000 g/eq, 3,100 g/eq, 3,200 g/eq, 3,300 g/eq, 3,400 g/eq, 3,500 g/eq, 3,600 g/eq, 3,700 g/eq, 3,800 g/eq, 3,900 g/eq, 4,000 g/eq, 4,100 g/eq, 4,200 g/eq, 4,300 g/eq, 4,400 g/eq, 4,500 g/eq, 4,600 g/eq, 4,700 g/eq, 4,800 g/eq, 4,900 g/eq, 5,000 g/eq, etc. In one embodiment, the epoxy equivalent (g/eq) of the epoxy resin is preferably 100 g/eq or more, more preferably 150 g/eq or more, and even more preferably 180 g/eq or more, in view of the high mass residual rate of the rosin-based resin. The higher the epoxy equivalent of the epoxy resin, the higher the mass residual rate tends to be. In one embodiment, the epoxy equivalent of the epoxy resin is preferably about 100 to 5,000 g/eq, more preferably about 150 to 1,000 g/eq, and even more preferably about 180 to 500 g/eq, in order to further improve the fluidity of the thermoplastic resin when melted.

The reaction components may contain alcohols in addition to the rosins and epoxy resins. Examples of the alcohols include the alcohols in the rosin esters. In one embodiment, the alcohols are preferably two or more selected from the group consisting of dihydric alcohols, trihydric alcohols, tetrahydric alcohols, and hexahydric alcohols, because the mass residual ratio of the rosin polyol is high.

The method for producing the rosin polyol is not particularly limited, and various known methods can be used. Specifically, for example, there is a method in which the rosins and epoxy resins are subjected to a ring-opening addition reaction at 120 to 300°C in a nitrogen stream in the presence or absence of a catalyst.

Examples of the catalyst include amine catalysts such as trimethylamine, triethylamine, tributylamine, benzyldimethylamine, pyridine, and 2-methylimidazole, quaternary ammonium salts such as benzyltrimethylammonium chloride, Lewis acids, boric acid esters, organometallic compounds, organometallic salts, trialkylphosphines, and triarylphosphines.

In the above ring-opening addition reaction, a solvent may be used as necessary. There are no particular limitations on the solvent, so long as it is inert to the reaction and easily dissolves the raw materials and products. Specific examples include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-hexane; and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane.

In one embodiment, the amount of the rosins and epoxy resins used is usually such that, assuming that one epoxy group in the epoxy resin is equivalent to two OH groups, the OH groups of the epoxy resin (total of the OH groups present in the epoxy groups and the epoxy resin) / COOH groups of the rosins (equivalent ratio) is about 0.8 to 22, and preferably about 0.8 to 10 because the mass residual rate in the rosin-based resin is high.

In one embodiment, the rosin-based resin is preferably at least one selected from the group consisting of the rosin esters and rosin polyols, from the viewpoints of suppressing smoke generation when the thermoplastic resin is melted and improving the fluidity of the thermoplastic resin when melted, and more preferably the rosin esters, from the same viewpoints.

(Physical properties of rosin-based resin)
The mass residual ratio of the rosin-based resin is, for example, 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%, 83 mass%, 82 mass%, 81 mass%, 80 mass%, 79 mass%, 78 mass%, 77 mass%, 76 mass%, 75 mass%, 74 mass%, 73 mass%, 72 mass%, 7 ... Examples of the mass residual ratio include 1 mass%, 70 mass%, 69 mass%, 68 mass%, 67 mass%, 66 mass%, 65 mass%, 64 mass%, 63 mass%, 62 mass%, 61 mass%, 60 mass%, 59 mass%, 58 mass%, 57 mass%, 56 mass%, 55 mass%, 54 mass%, 53 mass%, 52 mass%, 51 mass%, 50 mass%, 49 mass%, 48 mass%, 47 mass%, 46 mass%, 45 mass%, 44 mass%, 43 mass%, 42 mass%, 41 mass%, 40 mass%, etc. In one embodiment, the mass residual ratio of the rosin-based resin is preferably 40 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, even more preferably 90 mass% or more, and particularly preferably 100 mass% from the viewpoint of suppressing smoke generation during melting of the thermoplastic resin. The higher the mass residual ratio of the rosin-based resin, the more effectively it is possible to suppress smoke generation during melting of the thermoplastic resin.

In this disclosure, the mass retention rate is measured by the method described in the Examples below.

Thermoplastic resins, particularly engineering plastics and super engineering plastics, are often processed at temperatures of 250°C or higher. The inventors of the present invention have hypothesized that when a modifier containing a rosin-based resin is used in a thermoplastic resin and smokes when melted, the rosin-based resin has many components that can volatilize and structures that can thermally decompose at the processing temperature, and that the smoke is generated by the volatile components and thermal decomposition products. The inventors of the present invention have evaluated the mass retention rate of rosin-based resins under harsh conditions of heating at a temperature (300°C) equal to or higher than the processing temperature for a long period of time (2 hours), and have found that those with a mass retention rate of 40% or higher have few such components and structures, and therefore smoke generation is suppressed even when used in the processing of thermoplastic resins.

In addition, since it is difficult to specify the details of rosin-based resins, such as the components that can volatilize at molding processing temperatures and the structures that can thermally decompose, the inventors have specified rosin-based resins that can suppress smoke generation when the thermoplastic resin is melted by defining the rosin-based resins at the above-mentioned mass residual ratio.

When the heating temperature is lower than 300°C and/or the heating time is shorter than 2 hours at the above mass retention rate, the heating conditions are mild, making it difficult to properly evaluate the tendency of rosin-based resins to emit smoke when the thermoplastic resin is melted. In addition, when the thermoplastic resin emits smoke when melted, the smoke causes equipment and mold contamination, but when the heating time is shorter than 2 hours, it is difficult to properly evaluate the degree of contamination because it is not possible to reflect the equipment and mold contamination that occurs in actual molding processing.

If the mass residual rate of the rosin-based resin is less than 40 mass%, when it is used in a thermoplastic resin, it tends to emit a lot of smoke when melted.

The MMAP of the rosin-based resin may be, for example, 20°C, 19°C, 18°C, 17°C, 15°C, 14°C, 13°C, 12°C, 11°C, 10°C, 9°C, 8°C, 7°C, 6°C, 5°C, 4°C, 3°C, 2°C, 1°C, 0°C, -1°C, -2°C, -3°C, -4°C, -5°C, -6°C, -7°C, -8°C, -9°C, or -10°C. In one embodiment, the MMAP of the rosin-based resin is preferably -10 to 20°C, more preferably -8 to 18°C, in order to improve the fluidity of the thermoplastic resin when melted.

Note that in this disclosure, the above MMAP is measured by the method described in the Examples below.

If the MMAP of the rosin-based resin is less than -10°C or more than 20°C, the flowability of the thermoplastic resin when melted tends to decrease.

The rosin-based resin is not particularly limited in terms of physical properties other than the mass residual rate and MMAP. Examples of the color tone of the rosin-based resin include 400 Hazen, 350 Hazen, 300 Hazen, 250 Hazen, 200 Hazen, 150 Hazen, 100 Hazen, 95 Hazen, 90 Hazen, 85 Hazen, 80 Hazen, 75 Hazen, 70 Hazen, 65 Hazen, 60 Hazen, 55 Hazen, 50 Hazen, 45 Hazen, 40 Hazen, 35 Hazen, 30 Hazen, 25 Hazen, 20 Hazen, 15 Hazen, 10 Hazen, and 5 Hazen. In one embodiment, the color tone of the rosin-based resin is preferably about 10 to 400 Hazen, and more preferably about 10 to 200 Hazen, in terms of suppressing coloring. In this disclosure, color tone is measured in Hazen units according to JIS K 0071-1, and in Gardner units according to JIS K 0071-2.

The acid value (mgKOH/g) of the rosin-based resin is, for example, 200 mgKOH/g, 195 mgKOH/g, 190 mgKOH/g, 185 mgKOH/g, 180 mgKOH/g, 175 mgKOH/g, 170 mgKOH/g, 165 mgKOH/g, 160 mgKOH/g, 155 mgKOH/g, 150 mgKOH/g, 145 mgKOH/g, 140 mgKOH/g, 135 mgKOH/g, 130 mgKOH/g, 125 mgKOH/g, 120 mgKOH/g, 115 mgKOH/g, 110 mgKOH/g, 10 5mgKOH/g, 100mgKOH/g, 95mgKOH/g, 90mgKOH/g, 85mgKOH/g, 80mgKOH/g, 75mgKOH/g, 70mgKOH/g, 65mgKOH/g, 60mgKOH/g, 55mgKOH/g, 50mgKOH/g, 49mgKOH/g, 48mgKOH/g, 47mgKOH/g, 46mgKOH/g, 45mgKOH/g, 44mgKOH/g, 43mgKOH/g, 42mgKOH/g, 41mgKOH/g, 40mgKOH/g, 39mgKOH/g, 38mgKOH/g , 37mgKOH/g, 36mgKOH/g, 35mgKOH/g, 34mgKOH/g, 33mgKOH/g, 32mgKOH/g, 31mgKOH/g, 30mgKOH/g, 29mgKOH/g, 28mgKOH/g, 27mgKOH/g, 26mgKOH/g, 25mgKOH/g, 24mgKOH/g, 23mgKOH/g, 22mgKOH/g, 21mgKOH/g, 20mgKOH/g, 19mgKOH/g, 18mgKOH/g, 17mgKOH/g, 16mgKOH/g, 15mgKOH/g, 14mgKOH /g, 13 mgKOH/g, 12 mgKOH/g, 11 mgKOH/g, 10 mgKOH/g, 9 mgKOH/g, 8 mgKOH/g, 7 mgKOH/g, 6 mgKOH/g, 5 mgKOH/g, 4 mgKOH/g, 3 mgKOH/g, 2 mgKOH/g, 1 mgKOH/g, 0.9 mgKOH/g, 0.8 mgKOH/g, 0.7 mgKOH/g, 0.6 mgKOH/g, 0.5 mgKOH/g, 0.4 mgKOH/g, 0.3 mgKOH/g, 0.2 mgKOH/g, 0.1 mgKOH/g, and 0 mgKOH/g. In one embodiment, the acid value of the rosin resin is preferably 200 mgKOH/g or less, more preferably 50 mgKOH/g or less, even more preferably 20 mgKOH/g or less, even more preferably 15 mgKOH/g or less, even more preferably 10 mgKOH/g or less, even more preferably 0.1 mgKOH/g or less, and particularly preferably 0 mgKOH/g, in order to further suppress smoke generation during melting of the thermoplastic resin. In this disclosure, the acid value is a value measured according to JIS K0070.

The lower the acid value of the rosin-based resin, the more likely it is that decarboxylation of the rosin-based resin at high temperatures is suppressed, and the higher the mass retention rate. For the same reason, the lower the number of moles of carboxyl groups (COOH) contained in the rosin-based resin, the higher the mass retention rate.

The higher the acid value of the rosin-based resin, the lower the MMAP tends to be. Also, the more moles of carboxyl groups (COOH) contained in the rosin-based resin, the lower the MMAP tends to be.

The weight average molecular weight of the rosin-based resin may be, for example, 4,000, 3,900, 3,800, 3,700, 3,600, 3,500, 3,400, 3,300, 3,200, 3,100, 3,000, 2,900, 2,800, 2,700, 2,600, 2,500, 2,400, 2,300, 2,200, 2,100, 2,000, 1,900, 1,800, 1,700, 1,600, 1,500, 1,400, 1,300, 1,200, 1,100, 1,000, 900, 800, 700, 600, etc. In one embodiment, the weight average molecular weight of the rosin resin is preferably 600 or more, more preferably 700 or more, from the viewpoint of further suppressing smoke generation when the thermoplastic resin is melted, and more preferably 600 or more. In one embodiment, the weight average molecular weight of the rosin resin is preferably about 600 to 4,000, more preferably about 600 to 3,000, even more preferably about 600 to 2,500, and particularly preferably about 700 to 2,500, from the viewpoint of further suppressing smoke generation when the thermoplastic resin is melted and further improving the fluidity of the thermoplastic resin when melted. In this disclosure, the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

The higher the weight average molecular weight of the rosin-based resin, the higher the mass retention rate tends to be. Also, the higher the weight average molecular weight of the rosin-based resin, the higher the MMAP tends to be, and the lower the weight average molecular weight, the lower the MMAP tends to be.

In one embodiment, the rosin-based resin may contain any of various known additives, provided that the effects of the present invention are not impaired. Examples of additives include dehydrating agents, weathering agents, antioxidants, UV absorbers, heat stabilizers, and light stabilizers. The additives may be used alone or in combination of two or more.

(Additive)
In one embodiment, the modifier may contain any of various known additives as long as the effects of the present invention are not impaired. Examples of additives include dehydrating agents, weathering agents, antioxidants, UV absorbers, heat stabilizers, and light stabilizers. The additives may be used alone or in combination of two or more. In one embodiment, the content of the additive is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the rosin resin.

(Use of modifiers for thermoplastic resins)
The above-mentioned modifier can be used for various known thermoplastic resins. The thermoplastic resin may be used alone or in combination of two or more. Examples of the thermoplastic resin include those described below.

In one embodiment, the above modifier is preferably used for a thermoplastic resin containing at least one selected from the group consisting of polyamide, polycarbonate, polyphenylene ether, and polyolefin resin, and more preferably used for a thermoplastic resin containing at least one selected from the group consisting of polyamide 66, polyamide 6, polycarbonate, modified polyphenylene ether resin, polyethylene, and polypropylene, in order to further improve the fluidity during melting.

In one embodiment, the modifier contains the rosin-based resin, and is therefore preferably used for thermoplastic resins with high molding temperatures, particularly preferably for engineering plastics and super engineering plastics.

The amount of the modifier used is not particularly limited. For example, the amount of the modifier used may be 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 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 thermoplastic resin. In one embodiment, the amount of the modifier used is preferably 0.1 parts by mass or more per 100 parts by mass of the thermoplastic resin in order to improve the fluidity of the thermoplastic resin when melted, and is preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin in order to improve the fluidity of the thermoplastic resin when melted and to suppress smoke generation when melted. In one embodiment, the amount of the modifier used is preferably about 0.1 to 20 parts by mass, more preferably about 0.1 to 10 parts by mass, and even more preferably about 0.5 to 5 parts by mass in order to improve the fluidity of the thermoplastic resin when melted and to suppress smoke generation when melted.

In addition, when a filler described below is used in combination with the thermoplastic resin, the amount of the modifier used may be, for example, 20 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight, 12 parts by weight, 11 parts by weight, 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight, 0.9 parts by weight, 0.8 parts by weight, 0.7 parts by weight, 0.6 parts by weight, 0.5 parts by weight, 0.4 parts by weight, 0.3 parts by weight, 0.2 parts by weight, 0.1 parts by weight, etc., per 100 parts by weight of the thermoplastic resin. In one embodiment, when a filler described later is used in combination with the thermoplastic resin, the amount of the modifier used is preferably 0.1 parts by mass or more per 100 parts by mass of the thermoplastic resin in order to improve the fluidity of the thermoplastic resin when melted, and is preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin in order to improve the fluidity of the thermoplastic resin when melted and to suppress smoke generation when the thermoplastic resin is melted. In one embodiment, when a filler described later is used in combination with the thermoplastic resin, the amount of the modifier used is preferably about 0.1 to 20 parts by mass in order to improve the fluidity of the thermoplastic resin when melted and to suppress smoke generation when the thermoplastic resin is melted, and is more preferably about 0.5 to 15 parts by mass, and even more preferably about 5 to 10 parts by mass.

In addition, when the modifier is used in a thermoplastic resin containing a filler, which will be described later, it can improve the mechanical properties of a molded body of the thermoplastic resin compared to when the modifier is not used. Although the details are unclear, it is presumed that the modifier improves the interfacial adhesion between the thermoplastic resin and the filler, thereby improving the mechanical properties of the molded body.

The method of using the modifier is not particularly limited. For example, the modifier is added to a mixer together with a thermoplastic resin, and melt-kneaded in the mixer. Examples of the mixer include a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. The temperature of the melt-kneading is not particularly limited, but is usually in the range of the melting point of the thermoplastic resin -30°C to the melting point +30°C.

[Resin composition]
The present disclosure relates to a resin composition containing the above-mentioned modifier (or the above-mentioned rosin-based resin) and a thermoplastic resin.

<Thermoplastic resin>
The thermoplastic resin is not particularly limited, and various known thermoplastic resins can be used. The thermoplastic resins may be used alone or in combination of two or more.

Examples of the thermoplastic resin include polyolefin resins, styrene resins, ABS resins, polyamides, polyesters, polycarbonates, polyacetals, phenoxy resins, polymethyl methacrylate resins, polyphenylene ethers, polyphenylene sulfides, polyamide-imides, polyimides, polyether-imides, liquid crystal polymers, polyether-ether ketones, polyether-sulfones, polysulfones, polyarylates, and fluororesins.

(Polyolefin resin)
The polyolefin resin is not particularly limited, and various known polyolefin resins can be used. The polyolefin resins may be used alone or in combination of two or more.

The polyolefin resins include, for example, homopolymers of α-olefins having about 2 to 8 carbon atoms, such as ethylene, propylene, and 1-butene; binary or ternary (co)polymers of the above-mentioned α-olefins; binary or ternary (co)polymers of the above-mentioned α-olefins with α-olefins having about 9 to 18 carbon atoms, conjugated dienes, non-conjugated dienes, unsaturated carboxylic acids, (meth)acrylic acid esters, vinyl acetate, and the like.

Examples of the α-olefins having about 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 conjugated dienes and non-conjugated dienes include butadiene, isoprene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene. Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated carboxylic acids may be neutralized with a base or the like. Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, isooctyl (meth)acrylate, etc. Two or more of these α-olefins, conjugated dienes, non-conjugated dienes, unsaturated carboxylic acids, and (meth)acrylic acid esters may be used.

The polyolefin resins include, for example, ethylene resins such as polyethylene, 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; propylene resins such as polypropylene, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-4-methyl-1-pentene copolymer, and propylene-ethylene-1-hexene copolymer; 1-butene resins such as 1-butene homopolymer, 1-butene-ethylene copolymer, and 1-butene-propylene copolymer; and 4-methyl-1-pentene resins such as 4-methyl-1-pentene homopolymer and 4-methyl-1-pentene-ethylene copolymer.

(styrene resin)
The styrene-based resin is not particularly limited, and various known styrene-based resins can be used. The styrene-based resins may be used alone or in combination of two or more.

Examples of the styrene resin include resins obtained by polymerizing a styrene compound and, if necessary, other compounds copolymerizable therewith in the presence or absence of a rubber polymer. Examples of the styrene compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene, and the like. Examples of other compounds copolymerizable with the styrene compound include vinyl cyanide compounds, acrylic acid esters, methacrylic acid esters, epoxy group-containing methacrylic acid esters, maleimide compounds, α,β-unsaturated carboxylic acids and their anhydrides, and the like. Examples of the rubber polymer include polybutadiene, polyisoprene, diene copolymers, copolymers of ethylene and α-olefins, copolymers of ethylene and unsaturated carboxylic acid esters, ethylene, propylene, and non-conjugated diene terpolymers, and acrylic rubbers. The styrene-based compound, the other compound copolymerizable with the styrene-based compound, and the rubber polymer may be used alone or in combination of two or more. In one embodiment, the styrene-based resin is preferably polystyrene.

(polyamide)
The polyamide is not particularly limited, and various known polyamides can be used. The polyamides may be used alone or in combination of two or more.

The polyamide is a resin made of a polymer having an amide bond, and is made from amino acids, lactams, or diamines and dicarboxylic acids as the main raw materials. The polyamide may be a polyamide homopolymer or copolymer derived from these raw materials, either alone or in the form of a mixture. Two or more of these raw materials may also be used in combination.

Examples of the above amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid.

Examples of the lactams include ε-caprolactam and ω-laurolactam.

Examples of the diamines include aliphatic diamines, aromatic diamines, alicyclic diamines, etc. Examples of the aliphatic diamines include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 2-methylpentamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4-/2,4,4-trimethylhexamethylene diamine, 5-methylnonamethylene diamine, etc. Examples of the aromatic diamines include metaxylylene diamine, paraxylylene diamine, etc. Examples of alicyclic diamines include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, and aminoethylpiperazine.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids. Examples of the aliphatic dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. Examples of the alicyclic dicarboxylic acids include hexahydroterephthalic acid and hexahydroisophthalic acid.

The above polyamide resins include, for example, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610), polypentamethylene sebacamide (polyamide 510), polyhexamethylene dodecamide (polyamide 612), and polyundecane amide (polyamide 11). , polydodecanamide (polyamide 12), polynonane terephthalamide (polyamide 9T), polycaproamide/polyhexamethylene terephthalamide copolymer (polyamide 6/6T), polyhexamethylene adipamide/polyhexamethylene terephthalamide copolymer (polyamide 66/6T), polyhexamethylene adipamide/polyhexamethylene isophthalamide copolymer (polyamide 66/6I), polyhexamethylene adipamide/ Polyhexamethylene isophthalamide/polycaproamide copolymer (polyamide 66/6I/6), polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (polyamide 6T/6I), polyhexamethylene terephthalamide/polydodecanamide copolymer (polyamide 6T/12), polyhexamethylene adipamide/polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (polyamide Polyamide 66/6T/6I), polyxylylene adipamide (polyamide XD6), polymetaxylylene adipamide (polyamide MXD6), polyhexamethylene terephthalamide/poly-2-methylpentamethylene terephthalamide copolymer (polyamide 6T/M5T), polyhexamethylene terephthalamide/polypentamethylene terephthalamide copolymer (polyamide 6T/5T), and mixtures or copolymers thereof.

In one embodiment, the polyamide is preferably polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 9T, polyamide 6/66 copolymer, polyamide 6/12 copolymer, and from the same viewpoint, more preferably polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 9T.

(polyester)
The polyester is not particularly limited, and various known polyesters can be used. The polyester may be used alone or in combination of two or more.

The polyester may be a polymer or copolymer obtained by a condensation reaction of a polycarboxylic acid (or an ester-forming derivative thereof) and a polyhydric alcohol (or an ester-forming derivative thereof) as the main components, or a mixture thereof. In addition, two or more types of polycarboxylic acids and polyhydric alcohols may be used in combination.

The polycarboxylic acids include, for example, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, tricarboxylic acids, and ester-forming derivatives thereof. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and 5-sodium sulfoisophthalic acid. Examples of aliphatic dicarboxylic acids include adipic acid, sebacic acid, azelaic acid, and dodecanedioic acid. Examples of alicyclic dicarboxylic acids include 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples of tricarboxylic acids include trimellitic acid.

The polyhydric alcohols include, for example, aliphatic glycols, alicyclic diols, aromatic diols, trimethylolpropane, pentaerythritol, glycerol, and ester-forming derivatives thereof. The aliphatic glycols include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol. The alicyclic diols include, for example, cyclopentanediol, cyclohexanediol, and hydrogenated bisphenol A. The aromatic diols include, for example, bisphenol A ethylene oxide (1 mol to 100 mol) adducts, bisphenol A propylene oxide (1 mol to 100 mol) adducts, and xylene glycol.

Examples of the polyester include polybutylene terephthalate, polybutylene (terephthalate/isophthalate), polybutylene (terephthalate/adipate), polybutylene (terephthalate/sebacate), polybutylene (terephthalate/decanedicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate/isophthalate), polyethylene (terephthalate/adipate), polyethylene (terephthalate/5-sodium sulfoisophthalate), polybutylene (terephthalate/5-sodium sulfoisophthalate), polyethylene naphthalate, and polycyclohexanedimethylene terephthalate.

In one embodiment, the polyester is preferably polybutylene terephthalate, polybutylene (terephthalate/adipate), polybutylene (terephthalate/decanedicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate/adipate), polyethylene naphthalate, or polycyclohexanedimethylene terephthalate, more preferably polyethylene terephthalate or polybutylene terephthalate.

(Polycarbonate)
The polycarbonate is not particularly limited, and various known polycarbonates can be used. The polycarbonates may be used alone or in combination of two or more.

The polycarbonate may be, for example, one obtained by reacting an aromatic dihydroxy compound with a carbonate precursor. The polycarbonate may be linear or may have a branched structure.

The aromatic dihydroxy compounds include, for example, bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxydiaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, hydroquinones, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzophenone, etc. The aromatic dihydroxy compounds may be used alone or in combination of two or more.

Examples of the bis(hydroxyaryl)alkanes include 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol A), tetrabromobisphenol A, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)dec ... , 1-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, etc.

Examples of the bis(hydroxyaryl)cycloalkane include 1,1-bis(4-hydroxyphenyl)cyclohexane (also known as bisphenol Z), 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclooctane, and 9,9-bis(4-hydroxyphenyl)fluorene.

The dihydroxydiaryl ethers include, for example, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, etc. The dihydroxydiaryl sulfides include, for example, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, etc. The dihydroxydiaryl sulfoxides include, for example, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, etc. The dihydroxydiaryl sulfones include, for example, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, etc.

The carbonate precursor may be, for example, a carbonyl halide, a carbonic acid diester, etc. One type of carbonate precursor may be used alone, or two or more types may be used in combination.

The carbonyl halides include, for example, phosgene; haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds. The carbonyl halides may be used alone or in combination of two or more.

The above carbonic acid diesters include, for example, diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, and dinaphthyl carbonate; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, di-tert-butyl carbonate, and dicyclohexyl carbonate; biscarbonates of dihydroxy compounds, carbonates of dihydroxy compounds such as cyclic carbonates, and the like. One type of carbonic acid ester may be used alone, or two or more types may be used in combination.

The above-mentioned polycarbonates can be produced, for example, by interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

The polycarbonate may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), or a polyester carbonate resin copolymerized with such a bifunctional carboxylic acid and a bifunctional alcohol. Two or more of these polycarbonates may be used.

(Polyphenylene ether)
The polyphenylene ether is not particularly limited, and various known polyphenylene ethers can be used. The polyphenylene ethers may be used alone or in combination of two or more.

The polyphenylene ether may be, for example, a homopolymer or copolymer consisting of a repeating unit represented by the following general formula (1):

(In formula (1), R1, R2, R3, and R4 each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group, or an aryl group which may have a substituent, and n represents the number of repetitions.)

Examples of the homopolymer represented by the above general formula (1) include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly(2,6-dichloro-1,4-phenylene) ether, etc.

Examples of copolymers include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol.

The method for producing the polyphenylene ether is not particularly limited, and can be obtained by using various known means. Specific examples include the production methods described in U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357, and 3,257,358, JP-A-50-51197, JP-B-52-17880, and JP-B-63-152628, etc.

The polyphenylene ether may contain various other phenylene ether units as partial structures within the scope of the present invention. Examples of the phenylene ether units include 2-(dialkylaminomethyl)-6-methylphenylene ether units and 2-(N-alkyl-N-phenylaminomethyl)-6-methylphenylene ether units. In addition, a small amount of diphenoquinone or the like may be bonded to the main chain of the polyphenylene ether resin. Furthermore, it may be a polyphenylene ether resin modified with maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, anhydrides thereof, or unsaturated dicarboxylic acids in which one or two of the two carboxyl groups are esterified, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, styrene, epoxidized natural fats and oils, unsaturated alcohols of the general formula CnH2n-3OH (n is a positive integer) such as allyl alcohol, 4-penten-1-ol, and 1,4-pentadiene-3-ol, or unsaturated alcohols of the general formula CnH2n-5OH, CnH2n-7OH (n is a positive integer). These modified polyphenylene ether resins may be used alone or in combination of two or more. In addition, the melting point of the modified polyphenylene ether resin is defined as the peak top temperature of the peak observed in a temperature-heat flow graph obtained when the temperature is raised at 20°C/min in measurement with a differential scanning calorimeter (DSC), and if there are multiple peak top temperatures, it is defined as the highest temperature among them.

The polyphenylene ether may contain resin components other than polyphenylene ether, such as aromatic vinyl polymers and polyamides. Examples of aromatic vinyl polymers include atactic polystyrene, high impact polystyrene, syndiotactic polystyrene, styrene-maleic anhydride copolymers, styrene-butadiene copolymers, and acrylonitrile-styrene copolymers.

In one embodiment, when the polyphenylene ether is a mixture containing polyphenylene ether and polystyrene (so-called modified polyphenylene ether resin), the content of polyphenylene ether is typically 70% by mass or more, preferably 80% by mass or more, based on the total amount of polyphenylene ether and polystyrene.

Commercially available modified polyphenylene ether resins include, for example, "Iupiace" (registered trademark) manufactured by Mitsubishi Engineering Plastics Corporation, "NORYL" (registered trademark) manufactured by SABIC Corporation, and "Zylon" (registered trademark) manufactured by Asahi Kasei Corporation.

(Polyphenylene sulfide)
The polyphenylene sulfide is not particularly limited, and various known polyphenylene sulfides can be used. The polycarbonate may be used alone or in combination of two or more kinds.

The polyphenylene sulfide can be obtained, for example, by reacting a polyhalogenated aromatic compound with a sulfidizing agent in a polar organic solvent.

The polyhalogenated aromatic compound may, for example, be p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, or 1-methoxy-2,5-dichlorobenzene, with p-dichlorobenzene being preferred. It is also possible to combine two or more different polyhalogenated aromatic compounds to form a copolymer, but it is preferred to use a p-dihalogenated aromatic compound as the main component.

Examples of the sulfidizing agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide. Examples of the alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these, with sodium sulfide being preferred. Examples of the alkali metal hydrosulfides include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures of two or more of these, with sodium hydrosulfide being preferred. These alkali metal sulfides and hydrosulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides. The sulfidizing agents may be used alone or in combination of two or more.

The sulfidizing agent may also be an alkali metal sulfide prepared from an alkali metal hydrosulfide and an alkali metal hydroxide; or an alkali metal sulfide prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide.

It is also possible to use an alkali metal hydroxide and/or an alkaline earth metal hydroxide together with the sulfidizing agent. In one embodiment, the alkali metal hydroxide is preferably sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, or a mixture of two or more of these, and the alkaline earth metal hydroxide is, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, etc., and preferably sodium hydroxide.

The polyphenylene sulfide can be produced in high yields by recovering and post-treating. Specifically, it can be produced by the method of obtaining a polymer with a relatively small molecular weight described in JP-B-45-3368, or the method of obtaining a polymer with a relatively large molecular weight described in JP-B-52-12240 and JP-A-61-7332. The polyphenylene sulfide resin obtained by the above method can be used after various treatments such as crosslinking/polymerization by heating in air, heat treatment in an inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvents, hot water, acid aqueous solutions, and activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates, and functional group-containing disulfide compounds.

Commercially available polyphenylene sulfide products include, for example, "TORELINA" (registered trademark) manufactured by Toray Industries, Inc., "DIC.PPS" (registered trademark) manufactured by DIC Corporation, and "DURAFIDE" (registered trademark) manufactured by Polyplastics Co., Ltd.

(Liquid Crystal Polymer)
The liquid crystal polymer is not particularly limited, and various known liquid crystal polymers can be used. The liquid crystal polymer may be used alone or in combination of two or more kinds.

The liquid crystal polymer may be, for example, a liquid crystal polyester or a liquid crystal polyester amide. The liquid crystal polyester may be, but is not limited to, an aromatic polyester. In one embodiment, the liquid crystal polyester may be, for example, a fully aromatic polyester made using only aromatic compounds as raw material monomers. The liquid crystal polyester amide may be, but is not limited to, an aromatic polyester amide. In one embodiment, the liquid crystal polyester amide may be, for example, a fully aromatic polyester amide made using only aromatic compounds as raw material monomers. In addition, the liquid crystal polymer may be, for example, a polyester partially containing aromatic polyester or aromatic polyester amide in the same molecular chain.

The aromatic polyester is not particularly limited, but may be, for example,
(1) Polyesters consisting essentially of one or more aromatic hydroxycarboxylic acids and their derivatives;
(2) Mainly (a) one or more aromatic hydroxycarboxylic acids and their derivatives,
(b) a polyester composed of one or more of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof;
(3) Mainly (a) one or more aromatic hydroxycarboxylic acids and their derivatives,
(b) one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof;
(c) Polyesters composed of one or more of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof.

The aromatic polyester amide is not particularly limited, but may be, for example,
(1) Mainly (a) one or more aromatic hydroxycarboxylic acids and their derivatives,
(b) one or more of aromatic hydroxyamines, aromatic diamines, and derivatives thereof;
(c) a polyesteramide comprising one or more of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof;
(2) Mainly (a) one or more aromatic hydroxycarboxylic acids and their derivatives,
(b) one or more of aromatic hydroxyamines, aromatic diamines, and derivatives thereof;
(c) one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof;
(d) polyesteramides composed of one or more of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof. Furthermore, a molecular weight modifier may be used in combination with the above-mentioned components, if necessary.

The aromatic hydroxycarboxylic acid may be, for example, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, or 3-methyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid, or Examples of aromatic hydroxycarboxylic acids include alkyl, alkoxy, or halogen-substituted derivatives of aromatic hydroxycarboxylic acids such as 2-naphthoic acid, 2-chloro-4-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid, and 6-hydroxy-5,7-dichloro-2-naphthoic acid.

The above aromatic diols include, for example, aromatic diols such as 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxyterphenyl, hydroquinone, resorcinol, 2,6-naphthalenediol, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenoxy)ethane, 3,3'-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2-bis(4-hydroxyphenyl)propane, and bis(4-hydroxyphenyl)methane, as well as alkyl, alkoxy, or halogen-substituted aromatic diols such as chlorohydroquinone, methylhydroquinone, tert-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcinol, and 4-methylresorcinol.

The above aromatic dicarboxylic acids include, for example, aromatic dicarboxylic acids such as terephthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenylether-3,3'-dicarboxylic acid, diphenoxyethane-3,3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, and 1,6-naphthalenedicarboxylic acid, and alkyl, alkoxy, or halogen-substituted derivatives of the above aromatic dicarboxylic acids, such as chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, dimethylterephthalic acid, ethylterephthalic acid, methoxyterephthalic acid, and ethoxyterephthalic acid.

Examples of the aromatic hydroxyamine include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-1-naphthol, 4-amino-4'-hydroxybiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenylmethane, and 4-amino-4'-hydroxydiphenyl sulfide.
Examples of the aromatic diamine include 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine, N,N'-dimethyl-1,4-phenylenediamine, 4,4'-diaminophenyl sulfide (thiodianiline), 4,4'-diaminodiphenyl sulfone, 2,5-diaminotoluene, 4,4'-ethylenedianiline, 4,4'-diaminodiphenoxyethane, 4,4'-diaminodiphenylmethane (methylenedianiline), and 4,4'-diaminodiphenyl ether (oxydianiline).

In one embodiment, the aromatic polyester is more preferably an aromatic polyester having the aromatic hydroxycarboxylic acid as a constituent component. In one embodiment, the aromatic polyester amide is more preferably an aromatic polyester amide having the aromatic hydroxycarboxylic acid as a constituent component.

The method for producing the liquid crystal polymer is not particularly limited, and can be obtained by using various known means. Specifically, for example, the liquid crystal polymer can be produced by known methods such as direct polymerization or transesterification using the above-mentioned raw material monomer compound (or a mixture of raw material monomers). Usually, melt polymerization, solution polymerization, slurry polymerization, solid-phase polymerization, or a combination of two or more of these is used, and melt polymerization or a combination of melt polymerization and solid-phase polymerization is preferably used. In the case of a compound capable of forming an ester, it may be used in the polymerization in its original form, or it may be modified from a precursor to a derivative capable of forming an ester using an acylating agent or the like in a stage prior to polymerization. Examples of the acylating agent include carboxylic anhydrides such as acetic anhydride.

Various catalysts may be used in the polymerization. Examples of such catalysts include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris(2,4-pentanedionato)cobalt(III), and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The amount of catalyst used is usually about 0.001 to 1% by mass, and preferably about 0.01 to 0.2% by mass, based on the total mass of the monomers.

In one embodiment, the liquid crystal polymer is preferably a liquid crystal polyester, which provides a resin composition with excellent heat resistance and high strength, and more preferably a wholly aromatic polyester, which provides the same.

In one embodiment, the thermoplastic resin in the resin composition preferably includes at least one selected from the group consisting of polyamide, polycarbonate, polyphenylene ether, and polyolefin resin, and more preferably includes at least one selected from the group consisting of polyamide 66, polyamide 6, polycarbonate, modified polyphenylene ether resin, polyethylene, and polypropylene, in view of excellent fluidity when the resin composition is melted.

The resin composition contains the above-mentioned modifier, which suppresses smoke generation during melting and provides excellent fluidity during melting, even when the molding temperature is high, for example, when engineering plastics or super engineering plastics are used as the thermoplastic resin.

(Filler)
In one embodiment, the resin composition may optionally contain a filler. The filler is not particularly limited, and various known fillers can be used. The filler may be used alone or in combination of two or more.

The filler may be, for example, spherical, needle-like, fibrous, or plate-like.

The above-mentioned fillers include, for example, fibers, crystalline silica, fused silica, calcium silicate, silica sand, talc, kaolin, mica, clay, bentonite, sericite, calcium carbonate, magnesium carbonate, glass beads, glass flakes, glass microballoons, molybdenum disulfide, wollastonite, calcium polyphosphate, graphite, metal powder, metal flakes, metal ribbons, metal oxides (alumina, zinc oxide, titanium oxide, etc.), cellulose powder (cellulose particles), carbon powder, graphite, carbon flakes, scaly carbon, carbon nanotubes, etc. Specific examples of metals constituting the metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

The above-mentioned fibers are not particularly limited, and various known fibers can be used. Examples of the above-mentioned fibers include glass fibers; alumina fibers; organic fibers such as polyester fibers, polyamide fibers, polyimide fibers, polyvinyl alcohol modified fibers, polyvinyl chloride fibers, polyolefin (polyethylene, polypropylene) fibers, fluororesin fibers, polybenzimidazole fibers, acrylic fibers, phenolic fibers, polyamide fibers, aramid fibers, cellulose (nano) fibers, liquid crystal polymer (liquid crystal polyester, liquid crystal polyester amide) fibers, polyether ketone fibers, polyether sulfone fibers, polyphenylene ether fibers, and polyphenylene sulfide fibers; and metal fibers made of metals such as iron, gold, silver, copper, aluminum, brass, and stainless steel. The above-mentioned fibers may be used alone or in combination of two or more types.

In one embodiment, the fibers preferably include at least one type selected from the group consisting of glass fibers and organic fibers, and more preferably include at least one type selected from the group consisting of glass fibers and cellulose fibers.

In one embodiment, the filler preferably contains at least one selected from the group consisting of glass fiber, carbon powder, calcium carbonate, cellulose powder, and cellulose fiber, in order to provide excellent mechanical properties to the resin composition.

In the past, in resin compositions containing the above-mentioned fillers, the melt viscosity of the resin composition was very high due to the fillers, which sometimes resulted in extremely poor moldability. However, the resin composition of the present disclosure uses the above-mentioned modifier, which reduces the melt viscosity even when the resin composition contains the above-mentioned fillers, resulting in excellent moldability.

In addition, when the resin composition contains the filler, the use of the modifier improves the mechanical properties of the molded article compared to when no modifier is used. Although the details are unclear, it is presumed that the modifier improves the interfacial adhesion between the thermoplastic resin and the filler, improving the mechanical properties of the molded article.

(Additive)
In one embodiment, the resin composition may contain any additives as long as the effects of the present invention are not impaired. Examples of the additives include flame retardants, electrical conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration dampers, antibacterial agents, insect repellents, deodorants, coloring inhibitors, heat stabilizers, release agents, antistatic agents, plasticizers, colorants, dyes, foaming agents, foam inhibitors, coupling agents, inorganic pigments, organic pigments, flow improvers other than the rosin-based resins, and light stabilizers.

(Content of each ingredient)
When the resin composition does not contain the filler, the content of the modifier in the resin composition is not particularly limited.The content of the modifier in the resin composition is, for example, 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 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 thermoplastic resin. In one embodiment, the content of the modifier in the resin composition is preferably 0.1 parts by mass or more relative to 100 parts by mass of the thermoplastic resin from the viewpoint of excellent fluidity when the resin composition is melted, and is preferably 20 parts by mass or less relative to 100 parts by mass of the thermoplastic resin from the viewpoint of excellent fluidity when the resin composition is melted and smoke generation when the resin composition is melted is further suppressed. In one embodiment, the content of the modifier in the resin composition is preferably about 0.1 to 20 parts by mass from the viewpoint of excellent fluidity when the resin composition is melted and smoke generation when the resin composition is melted is further suppressed, more preferably about 0.1 to 10 parts by mass, and even more preferably about 0.5 to 5 parts by mass.

When the resin composition contains the filler, the content of the modifier in the resin composition is not particularly limited. The content of the modifier in the resin composition may be, for example, 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 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 thermoplastic resin. In one embodiment, when the resin composition contains the filler, the content of the modifier in the resin composition is preferably 0.1 parts by mass or more per 100 parts by mass of the thermoplastic resin in order to provide a resin composition with excellent fluidity when melted, and is preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin in order to provide a resin composition with excellent fluidity when melted and to further suppress smoke generation when melted. In one embodiment, the content of the modifier in the resin composition is preferably about 0.1 to 20 parts by mass in order to provide a resin composition with excellent fluidity when melted and to further suppress smoke generation when melted, and is more preferably about 0.5 to 15 parts by mass, and even more preferably about 2 to 10 parts by mass.

When the resin composition does not contain the filler, the content of the rosin-based resin in the resin composition is not particularly limited. The content of the rosin-based resin in the resin composition may be, for example, 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 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 thermoplastic resin. In one embodiment, the content of the rosin-based resin in the resin composition is preferably 0.1 parts by mass or more per 100 parts by mass of the thermoplastic resin in order to provide superior fluidity when the resin composition is melted, and is preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin in order to provide superior fluidity when the resin composition is melted and to further suppress smoke generation when the resin composition is melted. In one embodiment, the content of the rosin-based resin in the resin composition is preferably about 0.1 to 20 parts by mass in order to provide superior fluidity when the resin composition is melted and to further suppress smoke generation when the resin composition is melted, and is more preferably about 0.1 to 10 parts by mass, and even more preferably about 0.5 to 5 parts by mass.

When the resin composition contains the filler, the content of the rosin-based resin in the resin composition is not particularly limited. The content of the rosin-based resin in the resin composition may be, for example, 20 parts by mass, 19 parts by mass, 18 parts by mass, 17 parts by mass, 16 parts by mass, 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 thermoplastic resin. In one embodiment, when the resin composition contains the filler, the content of the rosin-based resin in the resin composition is preferably 0.1 parts by mass or more per 100 parts by mass of the thermoplastic resin in order to provide a resin composition with excellent fluidity when melted, and is preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin in order to provide a resin composition with excellent fluidity when melted and to further suppress smoke generation when melted. In one embodiment, the content of the rosin-based resin in the resin composition is preferably about 0.1 to 20 parts by mass, more preferably about 0.5 to 15 parts by mass, and even more preferably about 2 to 10 parts by mass in order to provide a resin composition with excellent fluidity when melted and to further suppress smoke generation when melted.

When the resin composition contains the filler, the content of the filler in the resin composition is not particularly limited. The content of the filler in the resin composition may be, for example, 150 parts by mass, 140 parts by mass, 130 parts by mass, 120 parts by mass, 110 parts by mass, 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 parts by mass, etc., relative to 100 parts by mass of thermoplastic resin. In one embodiment, the content of the filler in the resin composition is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, relative to 100 parts by mass of thermoplastic resin, in terms of excellent fluidity when the resin composition is melted.

The content of the additive in the resin composition is not particularly limited. The content of the additive in the resin composition may be, for example, 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., relative to 100 parts by mass of the resin composition. In one embodiment, the content of the additive in the 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, relative to 100 parts by mass of the 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.

(Method for producing resin composition)
The method for producing the resin composition is not particularly limited, and various known methods can be adopted. For example, the method for producing the resin composition includes a method in which the modifier (or the rosin-based resin), the thermoplastic resin, and, if necessary, the filler and the additives are mixed in advance using various mixers such as a tumbler mixer or a Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader. The temperature of the melt-kneading is not particularly limited, but is usually in the range of the melting point of the thermoplastic resin -30°C to the melting point +30°C.

In the production of the above resin composition, the use of the above modifier or the above rosin-based resin increases the fluidity of the resin composition when melt-kneaded, resulting in excellent productivity. Furthermore, in the production of resin compositions containing fillers, the filler makes the melt viscosity of the resin composition very high, resulting in an extremely low fluidity when melt-kneaded. However, when the above modifier or the above rosin-based resin is used, the fluidity of the resin composition when melt-kneaded is increased, even in the production of resin compositions containing fillers.

In addition, when producing the resin composition, even if the modifier or the rosin-based resin is used, smoke generation during melt kneading is suppressed.

[Molded body]
The molded article of the present disclosure can be obtained by molding the resin composition by various known molding methods. The shape of the molded article is not particularly limited and can be appropriately selected according to the use and purpose of the molded article, and examples thereof include plate-like, plate-like, rod-like, sheet-like, film-like, cylindrical, annular, circular, elliptical, polygonal, irregular, hollow, frame-like, box-like, and panel-like shapes.

The method for molding the molded body is not particularly limited, and any conventionally known molding method can be used. Specific examples include injection molding, injection compression molding, extrusion molding, stretch film molding, inflation molding, profile extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), press molding, rotational molding, multi-layer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding. Of these, it is preferable that molding is performed by injection molding. Examples of injection molding machines include well-known injection molding machines such as ultra-high speed injection molding machines and injection compression molding machines.

The above molded products can be used for a variety of purposes, including automobile parts, electrical and electronic parts, building materials, various containers, daily necessities, household goods, and sanitary products.

[Use as a modifier for thermoplastic resins]
The rosin-based resin can be used as a modifier for a thermoplastic resin. When the rosin-based resin is used in a thermoplastic resin, the flowability of the thermoplastic resin during melting is improved. The thermoplastic resin is not particularly limited, and examples thereof include those mentioned above.

In one embodiment, the rosin-based resin is preferably used as a modifier for a thermoplastic resin containing at least one selected from the group consisting of polyamide, polycarbonate, polyphenylene ether, and polyolefin-based resins, from the viewpoint of further improving the fluidity during melting, and more preferably used as a modifier for a thermoplastic resin containing at least one selected from the group consisting of polyamide 66, polyamide 6, polycarbonate, modified polyphenylene ether resin, polyethylene, and polypropylene.

In one embodiment, the rosin-based resin is preferably used as a modifier for thermoplastic resins with high molding temperatures, particularly preferably for engineering plastics and super engineering plastics.

The amount of the rosin-based resin used as a modifier for the thermoplastic resin is not particularly limited. Examples of the amount of the rosin-based resin used include the amount of the modifier used described above.

In addition, when the rosin-based resin is used as a modifier for a thermoplastic resin containing a filler, it can improve the mechanical properties of a molded body of the thermoplastic resin compared to when the rosin-based resin is not used. Although the details are unclear, it is presumed that the rosin-based resin improves the interfacial adhesion between the thermoplastic resin and the filler, thereby improving the mechanical properties of the molded body.

The present disclosure provides the following:
(Item A1)
The mass residual rate after heating at 300° C. for 2 hours is 40% by mass or more,
Mixed methylcyclohexaneaniline cloud point (MMAP) is -10 to 20°C;
Contains rosin-based resins
Modifier for thermoplastic resins.
(Item A2)
The modifier for thermoplastic resins according to the above item, wherein the rosin-based resin is at least one selected from the group consisting of rosin esters and rosin polyols.
(Item A3)
The thermoplastic resin modifier according to the above item, wherein the rosin esters are made from polyhydric alcohols having three or more hydroxyl groups.
(Item A4)
The modifier for thermoplastic resin according to any of the preceding items, wherein the rosin esters are at least one selected from the group consisting of hydrogenated rosin esters and disproportionated rosin esters.
(Item A5)
The modifier for thermoplastic resin according to any one of the preceding items, wherein the rosin polyol is made from an epoxy resin having a weight average molecular weight of 150 to 2,000.
(Item A6)
The modifier for thermoplastic resin according to any one of the preceding items, wherein the rosin-based resin has a mass residual rate of 70 mass% or more after heating at 300°C for 2 hours.
(Item A7)
The modifier for thermoplastic resin according to any of the preceding items, wherein the rosin-based resin has a mixed methylcyclohexaneaniline cloud point (MMAP) of -8 to 18°C.
(Item A8)
2. The modifier for thermoplastic resin according to any one of the preceding items, wherein the rosin-based resin has a color tone of 10 to 200 Hazen.
(Item A9)
2. The thermoplastic resin modifier according to claim 1, wherein the rosin resin has an acid value of 200 mg KOH/g or less.
(Item A10)
2. The thermoplastic resin modifier according to claim 1, wherein the rosin resin has an acid value of 50 mg KOH/g or less.
(Item A11)
2. The thermoplastic resin modifier according to claim 1, wherein the rosin resin has an acid value of 20 mg KOH/g or less.
(Item A12)
2. The thermoplastic resin modifier according to claim 1, wherein the rosin resin has an acid value of 15 mg KOH/g or less.
(Item A13)
2. The thermoplastic resin modifier according to claim 1, wherein the rosin resin has an acid value of 10 mgKOH/g or less.
(Item A14)
2. The thermoplastic resin modifier according to claim 1, wherein the rosin resin has an acid value of 0.1 mg KOH/g or less.
(Item A15)
The modifier for thermoplastic resin according to any of the preceding items, wherein the rosin-based resin has a weight average molecular weight of 600 to 4,000.
(Item A16)
The modifier for thermoplastic resin according to any of the preceding items, wherein the rosin-based resin has a weight average molecular weight of 600 to 3,000.
(Item A17)
The modifier for thermoplastic resin according to any one of the preceding items, wherein the rosin-based resin has a weight average molecular weight of 600 to 2,500.
(Item A18)
The modifier for thermoplastic resin according to any of the preceding items, wherein the rosin-based resin has a weight average molecular weight of 700 to 2,500.
(Item A19)
A resin composition comprising the modifier of any of the preceding items and a thermoplastic resin.
(Item A20)
The resin composition according to the above item, wherein the thermoplastic resin comprises at least one selected from the group consisting of polyamide, polycarbonate, polyphenylene ether and polyolefin resin.
(Item A21)
The resin composition of any of the preceding items, further comprising a filler.
(Item A22)
The resin composition according to the above item, wherein the filler comprises at least one selected from the group consisting of glass fiber, carbon powder, calcium carbonate, cellulose powder and cellulose fiber.
(Item A23)
The resin composition according to any one of the preceding items, wherein the content of the modifier is 0.1 to 10 parts by mass per 100 parts by mass of the thermoplastic resin.
(Item A24)
The content of the modifier is 0.5 to 15 parts by mass per 100 parts by mass of the thermoplastic resin, and the content of the filler is 120 parts by mass or less per 100 parts by mass of the thermoplastic resin.
(Item A25)
A molded article obtained by molding any one of the resin compositions described above.
(Item A26)
2. Use of the rosin-based resin according to any one of the preceding items as a modifier for use in a thermoplastic resin.
(Item A27)
The use of item A26, wherein the thermoplastic resin comprises at least one selected from the group consisting of polyamide, polycarbonate, polyphenylene ether and polyolefin resin.
(Item A28)
The use of the above item A26 or A27, wherein the thermoplastic resin further comprises a filler.
(Item A29)
The use of the above item A28, wherein the filler comprises at least one selected from the group consisting of glass fiber, carbon powder, calcium carbonate, cellulose powder and cellulose fiber.
(Item A30)
The use of any of the above items A26 to A29, wherein the amount of the rosin-based resin used is 0.1 to 10 parts by mass per 100 parts by mass of the thermoplastic resin.
(Item A31)
The use of any of the above items A28 to A30, wherein the amount of the rosin-based resin used is 0.5 to 15 parts by mass per 100 parts by mass of the thermoplastic resin, and the content of the filler is 120 parts by mass or less per 100 parts by mass of the thermoplastic resin.
(Item A32)
Use of the rosin-based resin according to any of the preceding items for producing a resin composition containing a thermoplastic resin.
(Item A33)
The use of item A32, wherein the thermoplastic resin comprises at least one selected from the group consisting of polyamide, polycarbonate, polyphenylene ether and polyolefin resin.
(Item A34)
The use of the above item A32 or A33, wherein the resin composition further comprises a filler.
(Item A35)
The use of the above item A34, wherein the filler comprises at least one selected from the group consisting of glass fiber, carbon powder, calcium carbonate, cellulose powder and cellulose fiber.
(Item A36)
The use of any one of the above items A32 to A35, wherein the amount of the rosin-based resin used is 0.1 to 10 parts by mass per 100 parts by mass of the thermoplastic resin.
(Item A37)
The use of any of the above items A34 to A36, wherein the amount of the rosin-based resin used is 0.5 to 15 parts by mass per 100 parts by mass of the thermoplastic resin, and the content of the filler is 120 parts by mass or less per 100 parts by mass of the thermoplastic resin.

The modifier for thermoplastic resins provided in this disclosure can be used in thermoplastic resins to improve their fluidity when melted, thereby improving their moldability. In addition, when used in thermoplastic resins, the modifier can also suppress smoke generation when melted.

The present invention will be described in more detail below with reference to examples of the present invention, but the present invention is not limited to these examples. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

<Production of Rosin Resin>
Production Example 1
A reaction apparatus equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube, and a pressure reducing device was charged with 1,000 parts of Chinese gum rosin (acid value 170.0 mg KOH/g, softening point 74° C., color tone 7 Gardner) and 0.3 parts of palladium carbon (palladium loading 5%, water content 50%) as a catalyst, and a disproportionation reaction was carried out by stirring at 275° C. for 5 hours under a nitrogen blanket, to obtain a disproportionated rosin with an acid value of 155.0 mg KOH/g and a color tone 7 Gardner. Next, the disproportionated rosin was distilled under a nitrogen blanket under a reduced pressure of 5 mmHg, and the obtained main fraction was used as a purified disproportionated rosin.

500 parts of the above purified disproportionated rosin (acid value 180.0 mg KOH/g, softening point 84°C, color tone 4 Gardner) was charged into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube, and a pressure reducing device, and the temperature was raised to 185°C under a nitrogen seal. 57 parts of glycerin were added at 200°C while melting and stirring, and the temperature was then raised to 280°C. An esterification reaction was carried out at the same temperature for 14 hours, yielding 522 parts of purified disproportionated rosin ester with an acid value of 2.8 mg KOH/g and color tone 5 Gardner.

A shaking autoclave was charged with 200 parts of the purified disproportionated rosin ester and 2.5 parts of palladium carbon. After oxygen was removed from the system, the system was pressurized to 100 kg/ ^cm2 with hydrogen and heated to 260° C., and a hydrogenation reaction was carried out at the same temperature for 3.5 hours to obtain a hydrogenated rosin ester having an acid value of 13.3 mgKOH/g and a weight average molecular weight of 730.

Production Example 2
200g of Chinese hydrogenated rosin (manufactured by Guangxi Wuzhou Richeng Forest Chemical Co., Ltd.), 2.5g of 5% palladium alumina powder (manufactured by N.E. Chemcat Co., Ltd.), and 200g of cyclohexane were charged into a 1L autoclave, and after removing oxygen from the system, the system was pressurized to 7MPa with hydrogen, and then heated to 210°C. After reaching the temperature, the system was repressurized and maintained at 9MPa, and hydrogenation reaction was carried out for 5 hours. After filtering out the solvent, cyclohexane was removed under reduced pressure to obtain 191g of rosin with an acid value of 172.0mgKOH/g. Next, 180g of rosin was charged into a reaction apparatus equipped with a stirrer, a cooling tube, and a nitrogen inlet tube, and after melting to 200°C, 22g of glycerin was charged and reacted at 280°C for 12 hours to obtain 173g of rosin ester with an acid value of 10.7mgKOH/g. A 1-L autoclave was charged with 170 g of the obtained rosin ester, 1.3 g of 5% palladium carbon (water content: 50%), and 170 g of cyclohexane, and after removing oxygen from the system, the system was pressurized to 7 MPa with hydrogen and then heated to 200° C. After reaching the temperature, the system was repressurized and maintained at 9 MPa, and a hydrogenation reaction was carried out for 5 hours. The solvent was filtered off, and then cyclohexane was removed under reduced pressure to obtain a hydrogenated rosin ester having an acid value of 10.6 mgKOH/g and a weight average molecular weight of 780.

Production Example 3
Chinese gum rosin having an acid value of 172.0 mgKOH/g, a softening point of 74°C and a color of Gardner 6 was distilled under a nitrogen blanket at a reduced pressure of 5 mmHg in a reaction apparatus equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube and a pressure reducing device, and the main fraction having general constants of an acid value of 175.0 mgKOH/g and a color of Gardner 4 was obtained as purified rosin.

600 g of the above purified rosin was charged into a reaction vessel equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube and pressure reducing device, and the temperature was raised to 185°C under a nitrogen blanket. 70 g of glycerin and 0.2 g of 5% palladium carbon (water content 50%) as a disproportionation catalyst were added at 200°C while melting and stirring, and the temperature was then raised to 280°C. Disproportionation and esterification reactions were carried out simultaneously at the same temperature for 11 hours, yielding a reaction product with an acid value of 2.9 mg KOH/g and a color of Gardner 4.

200 g of the above reaction product and 1.2 g of 5% palladium carbon (water content 50%) were charged into a 1-liter shaking autoclave, and after removing oxygen from within the system, the system was pressurized to 0.5 kg/cm2 with hydrogen and heated to 280°C. A dehydrogenation reaction was carried out at the same temperature for 4 hours, yielding a disproportionated rosin ester with an acid value of 9.0 mg KOH/g and a weight-average molecular weight of 720.

Production Example 4
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube and a water vapor inlet tube was charged with 100 parts of Chinese gum rosin and 5 parts of maleic anhydride, and reacted for 2 hours at 220°C under a nitrogen gas stream, after which 13.8 parts of pentaerythritol was charged and the temperature was raised to 280°C and reacted at the same temperature for 14 hours to complete the esterification. The reaction vessel was then depressurized to remove moisture and the like, yielding a maleic acid-modified rosin ester with an acid value of 42.0 mgKOH/g and a weight average molecular weight of 2,470.

Production Example 5
Chinese gum rosin having an acid value of 172.0 mgKOH/g, a softening point of 74°C and a color of Gardner 6 was distilled under a nitrogen blanket at a reduced pressure of 5 mmHg in a reaction apparatus equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube and a pressure reducing device, and the main fraction having general constants of an acid value of 175.0 mgKOH/g and a color of Gardner 4 was obtained as purified rosin.

100 parts of the purified rosin and 13.3 parts of pentaerythritol were charged into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube, and a pressure reducing device, and reacted at 250°C for 2 hours under a nitrogen gas flow, then heated to 275°C and reacted at the same temperature for 15 hours to complete the esterification. The pressure inside the reaction vessel was then reduced to remove moisture and other substances, yielding a purified rosin ester.

A shaking autoclave was charged with 200 parts of the purified rosin ester and 1 part of palladium carbon, and after removing oxygen from the system, the system was pressurized to 100 kg/ ^cm2 with hydrogen and heated to 260° C. A hydrogenation reaction was carried out at the same temperature for 3 hours to obtain a hydrogenated rosin ester having an acid value of 12.8 mgKOH/g and a weight average molecular weight of 1,000.

Production Example 6
In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube and a steam inlet tube, 100 parts of rosin (acid value 172 mgKOH/g, softening point 77°C) was charged and melted at 160°C. Next, 18 parts of fumaric acid was charged, the temperature was raised to 225°C, and the reaction was carried out at the same temperature for 2 hours. After that, 6 parts of glycerin was charged, the temperature was raised to 215°C, and the reaction was carried out at the same temperature for 3.5 hours, to obtain a fumaric acid-modified rosin ester having an acid value of 191.0 mgKOH/g and a weight average molecular weight of 3,220.

Production Example 7
A reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube, and water vapor inlet tube was
68 parts of polymerized rosin (acid value 150 mgKOH/g, softening point 142° C.) and 32 parts of rosin (acid value 172 mgKOH/g, softening point 77° C.) were charged and melted at 215° C. Next, 11.5 parts of pentaerythritol were charged, and the temperature was increased to 250° C. and reacted at the same temperature for 3 hours, and then the temperature was further increased to 275° C. and reacted at the same temperature for 9 hours. Thereafter, a polymerized rosin ester having an acid value of 6.6 mgKOH/g and a weight average molecular weight of 2,400 was obtained by subjecting it to a reduced pressure treatment for 4 hours.

Production Example 8
A reaction apparatus equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 200 parts of disproportionated rosin and heated under a nitrogen stream until completely melted, after which 113 parts of bisphenol A type polymeric epoxy resin (epoxy equivalent: 170) was added with stirring, and 0.1 part of 2-methylimidazole was added at 150° C. and the mixture was allowed to react at 160° C. for 4 hours to obtain a rosin polyol having an acid value of 0.1 mgKOH/g and a weight average molecular weight of 860.

Production Example 9
A reaction apparatus equipped with a thermometer, a stirrer, a cooling tube, and a nitrogen inlet tube was charged with 300 parts of disproportionated rosin and heated under a nitrogen stream until completely melted, after which 113 parts of bisphenol A type polymeric epoxy resin (epoxy equivalent: 170) was added with stirring, and 0.1 part of 2-methylimidazole was added at 150° C. and the mixture was allowed to react at 160° C. for 4 hours to obtain a rosin polyol having an acid value of 45.2 mgKOH/g and a weight average molecular weight of 720.

Comparative Production Example 1
Chinese gum rosin having an acid value of 172.0 mgKOH/g and a color tone of Gardner 6 was distilled under a nitrogen blanket at a reduced pressure of 5 mmHg in a reaction apparatus equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube, and a pressure reducing device, and the main fraction having general constants of an acid value of 175.0 mgKOH/g and a color tone of Gardner 4 was obtained as purified rosin.

100 parts of the purified rosin and 26 parts of fumaric acid were charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube, and water vapor inlet tube, and reacted for 3 hours at 225°C under a nitrogen gas stream. Then, 1.5 parts of ethylene glycol and 7.5 parts of pentaerythritol were charged and reacted for 13 hours at 250°C, yielding a fumaric acid-modified rosin ester with an acid value of 203.0 mg KOH/g and a weight average molecular weight of 1,240.

Comparative Production Example 2
1,000 parts of Chinese gum rosin (acid value 170, softening point 74°C, color tone 6 Gardner) and 500 parts of xylene were placed in a Kolben, heated and dissolved, after which about 350 parts of xylene was distilled off, then 350 parts of cyclohexane was added and cooled to room temperature. When about 100 parts of crystals were produced by cooling, the supernatant was transferred to another Kolben and further recrystallized at room temperature, after which the supernatant was removed and washed with 100 parts of cyclohexane, and the solvent was distilled off to obtain 700 parts of purified rosin.

Next, 660 parts of the 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 stream. Unreacted materials were then removed under reduced pressure to obtain 720 parts of an addition reaction product. Furthermore, 500 parts of the resulting addition reaction product and 5.0 parts of 5% palladium carbon (water content 50%) were charged into a 1-liter rotary autoclave, and after removing oxygen from the system, the system was pressurized to 10 MPa with hydrogen and heated to 220°C. A hydrogenation reaction was carried out at the same temperature for 3 hours to obtain a hydrogenated product of acrylic acid-modified rosin with an acid value of 240 mgKOH/g and a weight average molecular weight of 360.

Comparative Production Example 3
A reaction vessel equipped with a thermometer, a stirrer, a cooling tube, and a nitrogen inlet tube was charged with 500 parts of disproportionated rosin and heated under a nitrogen stream until completely melted. Then, 113 parts of bisphenol A type polymeric epoxy resin (epoxy equivalent: 170) was added with stirring, and 0.1 part of 2-methylimidazole was added at 150° C. and the mixture was allowed to react at 160° C. for 4 hours, yielding a rosin polyol having an acid value of 86.0 mgKOH/g and a weight average molecular weight of 550.

Comparative Example 4
1,000 parts of Chinese gum rosin (acid value 170, softening point 74°C, color tone 6 Gardner) and 500 parts of xylene were placed in a Kolben, heated and dissolved, after which about 350 parts of xylene was distilled off, then 350 parts of cyclohexane was added and cooled to room temperature. When about 100 parts of crystals were produced by cooling, the supernatant was transferred to another Kolben and further recrystallized at room temperature, after which the supernatant was removed and washed with 100 parts of cyclohexane, and the solvent was distilled off to obtain 700 parts of purified rosin.

Next, 660 parts of the purified rosin and 100 parts of acrylic acid were charged into a reaction vessel, and the mixture was reacted at 220°C for 4 hours while stirring under a nitrogen stream. After removing unreacted materials under reduced pressure, 5 parts of glycerin were added, and the mixture was heated to 280°C and reacted at the same temperature for 4 hours to complete the esterification. The reaction vessel was then depressurized to remove moisture and the like, thereby obtaining 725 parts of acrylic acid-modified rosin ester. Furthermore, 500 parts of the obtained acrylic acid-modified rosin ester and 5.0 parts of 5% palladium carbon (water content 50%) were charged into a 1-liter rotary autoclave, and after removing oxygen from the system, the system was pressurized to 10 MPa with hydrogen and heated to 220°C. The hydrogenation reaction was carried out at the same temperature for 3 hours, and a hydrogenated product of acrylic acid-modified rosin ester with an acid value of 226.5 mgKOH/g and a weight average molecular weight of 430 was obtained.

Comparative Production Example 5
100 parts of Chinese hydrogenated rosin (manufactured by Guangxi Wuzhou Richeng Forest Chemical Co., Ltd.) and 300 parts of methanol were charged into a 1L autoclave, and after removing oxygen from the system, the temperature was raised to 290°C. The internal pressure of the autoclave reached a maximum of 14 MPa. The reaction was allowed to proceed for 2 hours while blowing the contents every 20 minutes. The resulting reaction liquid was concentrated using a rotary evaporator, and then 5 parts of calcium hydroxide were added to perform simple distillation. After removing 6 parts of the initial fraction under conditions of a liquid temperature of 150 to 270°C and a pressure of 0.4 kPa, 65 parts of rosin methyl ester with an acid value of 1.0 mgKOH/g and a weight average molecular weight of 240 was obtained as the main fraction.

(Measurement of weight average molecular weight (Mw))
The weight average molecular weight (Mw) of the rosin resins of Production Examples 1 to 9 and Comparative Production Examples 1 and 3 to 5 was calculated as a polystyrene equivalent value obtained from a calibration curve of standard polystyrene by gel permeation chromatography (GPC). The GPC method was measured under the following conditions. The results are shown in Table 1.
Analytical device: HLC-8320 (manufactured by Tosoh Corporation)
Column: TSKgel Super HM-L x 3 Eluent: Tetrahydrofuran Injected sample concentration: 5 mg/mL
Flow rate: 0.6 mL/min
Injection volume: 40 μL
Column temperature: 40°C
Detector: RI

The weight average molecular weight (Mw) of the rosin resin of Comparative Production Example 2 was calculated as a polystyrene equivalent value from a calibration curve of standard polystyrene by gel permeation chromatography (GPC). The GPC method was measured under the following conditions. The results are shown in Table 1.
Analytical device: HLC-8320 (manufactured by Tosoh Corporation)
Column: TSK guard column H-H, TSK-GEL SUPER HM-L x 3 columns connected Eluent: Tetrahydrofuran Injected sample concentration: 5 mg/mL
Flow rate: 0.6 mL/min
Injection volume: 40 μL
Column temperature: 40°C
Detector: RI, UV (254 nm)

(Measurement of Acid Value)
The acid values of the rosin-based resins of Production Examples 1 to 9 and Comparative Production Examples 1 to 5 were measured in accordance with JIS K 0070. The results are shown in Table 1.

(Mass retention rate (%) after heating at 300°C for 2 hours)
The mass retention rate (%) of the rosin-based resins of Production Examples 1 to 9 and Comparative Production Examples 1 to 5 after heating at 300° C. for 2 hours was calculated by using a simultaneous differential thermal and gravimetric analyzer (manufactured by Hitachi High-Tech Science Corporation, device name "STA7200") under conditions of a nitrogen atmosphere, a sample mass of 10 mg, and a nitrogen flow rate of 250 ml/min, by raising the temperature from 30° C. to 300° C. at a rate of 10° C./min, and measuring the mass of the sample after heating at 300° C. for 2 hours, and then calculating the mass from (sample mass after heating)/(sample mass before heating)×100(%). The results are shown in Table 1.

Thermogravimetric differential thermal analysis (TG/DTA) and thermogravimetric analysis (TGA) can be used to measure the heat loss at temperatures of 1%, 3%, and 5% weight loss (1% weight loss temperature, 3% weight loss temperature, 5% weight loss temperature) at heating rates of 5°C/min and 10°C/min, etc. However, the inventors' investigations have revealed that these weight loss temperatures are not sufficient to adequately evaluate the tendency for rosin-based thermoplastic resins to emit smoke when melted.

For example, the 5% weight loss temperature of the rosin-based resin of Production Example 5 is 267°C, while the rosin-based resin of Comparative Production Example 2 has a 5% weight loss temperature of 256°C, so there is not a large difference between the two, but as can be seen from Table 1, the mass retention rate (%) after heating at 300°C for two hours is 86% for the rosin-based resin of Production Example 5, while it is 10% for the rosin-based resin of Comparative Production Example 2, showing a large difference. Also, as can be seen from Table 2 below, the pellets using the rosin-based resin of Production Example 5 suppressed smoke generation, but the pellets using the rosin-based resin of Comparative Production Example 2 generated a lot of smoke.

The 5% weight loss temperature of the rosin-based resins of Production Example 5 and Comparative Production Example 2 was measured using a simultaneous differential thermal and gravimetric analyzer (manufactured by Hitachi High-Tech Science Corporation, device name "STA7200") in a nitrogen atmosphere with a sample amount of 10 mg, a measurement temperature of 30 to 500°C, a heating rate of 10°C/min, and a nitrogen flow rate of 250 ml/min, to determine the temperature at which the sample weight decreased by 5%.

(Measurement of Mixed Methylcyclohexaneaniline Cloud Point (° C.) (MMAP))
The mixed methylcyclohexaneaniline cloud point (°C) (MMAP) of the rosin-based resins of Preparation Examples 1 to 9 and Comparative Preparation Examples 1 to 5 was measured by cooling a heated homogeneous solution of 1 g of each component, 1 mL of methylcyclohexane, and 2 mL of aniline, and measuring the temperature at which the solution became cloudy. The results are shown in Table 1.

The notes in Table 1 are as follows:
* Mass retention rate after heating at 300℃ for 2 hours

[Preparation of resin composition and molded article]
Example 1
100 parts of modified polyphenylene ether resin (manufactured by Global Polyacetal Corporation, product name "Iupiace AH40") and 3 parts of the rosin-based resin of Production Example 1 as a modifier were added to a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plastomill Model 10C100") and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 250° C. Thereafter, the kneaded product (resin composition) obtained was removed from the kneading device, hot pressed at 250° C., and formed into a sheet having a thickness of 1.0 mm, and cut into 5 mm x 5 mm pieces with a cutter to obtain pellets.

Example 2
The same preparation as in Example 1 was carried out to obtain pellets, except that in Example 1, 5 parts of the rosin-based resin of Production Example 1 was used as the modifier.

Examples 3 to 10
The same preparation as in Example 1 was carried out, except that the rosin-based resin in Production Example 1 was changed to the rosin-based resins in Production Examples 2 to 9 as the modifier, to obtain pellets.

Comparative Example 1
100 parts of modified polyphenylene ether resin (manufactured by Global Polyacetal Corporation, product name "Iupiace AH40") was put into a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plastomill Model 10C100") and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 250° C. Thereafter, the kneaded product (resin composition) obtained was removed from the kneading device, hot pressed at 250° C., and molded into a sheet with a thickness of 1.0 mm, and cut into 5 mm x 5 mm pieces with a cutter to obtain pellets.

Comparative Examples 2 to 6
The same preparation as in Example 1 was carried out, except that the rosin-based resin of Production Example 1 was replaced with the rosin-based resins of Comparative Production Examples 1 to 5 as the modifier, to obtain pellets.

(Smoke Generation Evaluation)
When the pellets of Examples 1 to 10 and Comparative Examples 1 to 6 were injection molded at 290°C using a Handtruder M-1 (a tabletop manual injection molding machine/pelletizer manufactured by Toyo Seiki Seisakusho Co., Ltd.), smoke generation during molding was visually evaluated and evaluated according to the following criteria. The results are shown in Table 2.
◯: Almost no smoke.
△: A small amount of smoke is generated.
×: A lot of smoke is emitted.

(Evaluation of MFR)
In accordance with JIS K 7210, the MFR of each of the pellets of Examples 1 to 10 and Comparative Examples 1 to 6 was measured under conditions of a temperature of 300° C. and a load of 21.2 N (2.16 kg).

The rate of increase in MFR of the pellets of Examples 1 to 10 and Comparative Examples 2 to 6 relative to the MFR of Comparative Example 1 (blank) was evaluated according to the following criteria. The results are shown in Table 2. The greater the rate of increase in MFR, the better the moldability, and a rating of ◯ indicates practical use without any problems.
◯: The increase in MFR compared to blank is 30% or more. △: The increase in MFR compared to blank is 10% or more but less than 30%. ×: The increase in MFR compared to blank is less than 10%.

The blending amounts in Table 2 are values in parts by mass. The abbreviations and notes in Table 2 are as follows.
*Since there was a lot of smoke and it was not possible to prepare pellets, the MFR was not measured.
mPPE: modified polyphenylene ether resin, product name "Iupiace AH40", manufactured by Global Polyacetal Co., Ltd.

[Preparation of resin composition and molded article]
Example 10
100 parts of polyamide (manufactured by Asahi Kasei Corporation, product name "Leona 1700S") and 5 parts of the rosin-based resin of Production Example 1 as a modifier were put into a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plastomill Model 10C100") and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 290° C. Thereafter, the kneaded product (resin composition) obtained was removed from the kneading device, hot pressed at 290° C., molded into a sheet having a thickness of 1.0 mm, and cut into 5 mm x 5 mm pieces with a cutter to obtain pellets.

Example 11
Example 10 was repeated to obtain pellets, except that 8 parts of the rosin resin of Production Example 1 was used as the modifier.

Examples 12 to 17
The same preparation as in Example 10 was carried out to obtain pellets, except that the rosin-based resin of Production Example 1 was replaced with the rosin-based resins of Production Examples 2 to 4, 6, and 8 to 9 as the modifier.

Comparative Example 7
100 parts of polyamide (manufactured by Asahi Kasei Corporation, product name "Leona 1700S") was put into a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plastomill Model 10C100") and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 290° C. Thereafter, the kneaded product (resin composition) obtained was removed from the kneading device, hot pressed at 290° C., and molded into a sheet having a thickness of 1.0 mm, and cut into 5 mm x 5 mm pieces with a cutter to obtain pellets.

Comparative Example 8
Example 10 was repeated to obtain pellets, except that the rosin resin of Production Example 1 was used as the modifier instead of the rosin resin of Comparative Production Example 5.

(Smoke Generation Evaluation)
When the pellets of Examples 10 to 17 and Comparative Examples 7 to 8 were injection molded at 290°C using a Handtruder M-1 (a tabletop manual injection molding machine/pelletizer manufactured by Toyo Seiki Seisakusho Co., Ltd.), smoke generation during molding was visually evaluated and evaluated according to the following criteria. The results are shown in Table 3.
◯: Almost no smoke.
△: A small amount of smoke is generated.
×: A lot of smoke is emitted.

(Evaluation of MFR)
In accordance with JIS K 7210, the MFR of each of the pellets of Examples 10 to 17 and Comparative Examples 7 to 8 was measured under conditions of a temperature of 290° C. and a load of 21.2 N (2.16 kg).

The increase rate of MFR of the pellets of Examples 10 to 17 and Comparative Example 8 relative to the MFR of Comparative Example 7 (blank) was evaluated according to the following criteria. The results are shown in Table 3. The larger the increase rate of MFR, the more excellent the moldability.
◯: The increase in MFR compared to blank is 300% or more. △: The increase in MFR compared to blank is 150% or more but less than 300%. ×: The increase in MFR compared to blank is less than 150%.

The blending amounts in Table 3 are values in parts by mass. The abbreviations and notes in Table 3 are as follows.
*Since there was a lot of smoke and it was not possible to prepare pellets, the MFR was not measured.
PA: Polyamide, product name "Leona 1700S", manufactured by Asahi Kasei Corporation

[Preparation of resin composition and molded article]
Example 18
70 parts of polypropylene (manufactured by SunAllomer Co., Ltd., product name "PMB60A"), 30 parts of cellulose fiber (manufactured by Rettenmeyer, product name "Arbocel BC1000"), and 5 parts of the rosin-based resin of Production Example 3 as a modifier were put into a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plastomill Model 10C100"), and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 190 ° C. Thereafter, the kneaded product (resin composition) obtained was taken out of the kneading device, hot pressed at 200 ° C., molded into a sheet with a thickness of 1.0 mm, and cut into 5 mm x 5 mm with a cutter to obtain pellets.

Examples 19 to 21
Example 18 was repeated to obtain pellets, except that the rosin resin of Production Example 3 was replaced with the rosin resins of Production Examples 6, 8 and 9 as the modifier.

Comparative Example 9
70 parts of polypropylene (manufactured by SunAllomer Co., Ltd., product name "PMB60A") and 30 parts of cellulose fiber (manufactured by Rettenmeyer, product name "Arbocel BC1000") were put into a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plastomill Model 10C100") and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 190°C. Thereafter, the kneaded product (resin composition) obtained was taken out of the kneading device, hot pressed at 200°C, molded into a sheet having a thickness of 1.0 mm, and cut into 5 mm x 5 mm pieces with a cutter to obtain pellets.

Comparative Examples 10 to 11
Example 18 was repeated to obtain pellets, except that the rosin resin of Production Example 3 was replaced with the rosin resins of Comparative Production Examples 1 and 5 as the modifier.

(Smoke Generation Evaluation)
When the pellets of Examples 18 to 21 and Comparative Examples 9 to 11 were injection molded at 200°C using a Handtruder M-1 (a tabletop manual injection molding machine/pelletizer manufactured by Toyo Seiki Seisakusho Co., Ltd.), smoke generation during molding was visually evaluated and evaluated according to the following criteria. The results are shown in Table 4.
◯: Almost no smoke.
△: A small amount of smoke is generated.
×: A lot of smoke is emitted.

(Evaluation of MFR)
In accordance with JIS K 7210, the MFR of each of the pellets of Examples 18 to 21 and Comparative Examples 9 to 11 was measured under conditions of a temperature of 190° C. and a load of 49.0 N (5 kg).

The increase rate of MFR of the pellets of Examples 18 to 21 and Comparative Examples 10 to 11 relative to the MFR of Comparative Example 9 (blank) was evaluated according to the following criteria. The results are shown in Table 4. The larger the increase rate of MFR, the more excellent the moldability.
◯: The increase in MFR compared to the blank was 100% or more. △: The increase in MFR compared to the blank was 50% or more but less than 100%. ×: The increase in MFR compared to the blank was less than 50%.

(Evaluation of bending stress)
The resin compositions of Examples 18 to 21 and Comparative Examples 9 to 11 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 prepare rectangular test pieces (length 80 mm x width 10 mm x thickness 4 mm). The prepared rectangular test pieces were subjected to bending stress (MPa) measurement in accordance with JIS K7171 using a Tensilon universal testing machine (product name "RTG-1210", manufactured by A&D Co., Ltd.) at a support distance of 64 mm, a test speed of 2 mm/min, a temperature of 23°C, and an RH environment of 50%. The results are shown in Table 4.

The blending amounts in Table 4 are values in parts by mass. The abbreviations and notes in Table 4 are as follows.
*Since there was a lot of smoke and it was not possible to prepare pellets, the MFR was not measured.
PP: Polypropylene, product name "PMB60A", manufactured by SunAllomer Co., Ltd. Cellulose: Cellulose fiber, product name "Arbocel BC1000", manufactured by Rettenmeyer

Claims

The mass residual rate after heating at 300° C. for 2 hours is 40% by mass or more,
The rosin-based resin has a mixed methylcyclohexaneaniline cloud point (MMAP) of -10 to 20°C.
Modifier for thermoplastic resins.
A resin composition comprising the modifier according to claim 1 and a thermoplastic resin.
The resin composition according to claim 2, wherein the thermoplastic resin comprises at least one selected from the group consisting of polyamide, polycarbonate, polyphenylene ether and polyolefin resin.
The resin composition according to claim 2 or 3, further comprising a filler.
The resin composition according to claim 4, wherein the filler comprises at least one selected from the group consisting of glass fiber, carbon powder, calcium carbonate, cellulose powder, and cellulose fiber.
Use of the rosin-based resin according to claim 1 as a modifier for use in thermoplastic resins.
The use according to claim 6, wherein the thermoplastic resin further comprises a filler.
Use of the rosin-based resin according to claim 1 for producing a resin composition containing a thermoplastic resin.
The use according to claim 8, wherein the resin composition further comprises a filler.