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

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

Technical Field

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

Background Art

[0002] Thermoplastic resins are industrially used in various fields. 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 heat resistance and strength balance. On the other hand, the above thermoplastic resins, especially engineering plastics and super engineering plastics, have a high molding processing temperature and many are inferior in melt fluidity. Therefore, usually, additives such as lubricants are added to thermoplastic resins to reduce the apparent flow viscosity during melting and improve the molding processability (Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Disclosure of the Invention

[0004] However, in thermoplastic resins, even when conventional lubricants are used, the fluidity during melting is still insufficient, and some are inferior in molding processability. Further, in thermoplastic resins, especially engineering plastics and super engineering plastics, since their melting points are as high as about 200°C or more, they are melted at a high temperature (250°C or more). However, when conventional lubricants are added, smoke may occur during melting.

[0005] Therefore, the present invention aims to provide a novel modifier for thermoplastic resins that can suppress smoke generation during the melting of thermoplastic resins and improve the moldability of thermoplastic resins.

[0006] As a result of diligent research, the inventors have found that the above problem can be solved by a modifier for thermoplastic resins containing a rosin-based resin that has a high mass residue rate after heating at 300°C for 2 hours and has a specific mixed methylcyclohexaneaniline cloud point (MMAP).

[0007] Furthermore, the present invention has been made to solve at least some of the above-mentioned problems and can be realized in the following embodiments or application examples.

[0008] (Item 1) The mass residue rate after heating at 300°C for 2 hours is 40% by mass or more. The mixed methylcyclohexaneaniline cloud point (MMAP) is -10 to 20°C. Contains rosin-based resins, A modifier for thermoplastic resins.

[0009] (Item 2) A resin composition comprising the modifier and thermoplastic resin described in item 1.

[0010] (Item 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.

[0011] (Item 4) Furthermore, the resin composition according to item 2 or 3, further comprising a filler.

[0012] (Item 5) The resin composition according to item 4, wherein the filler comprises at least one selected from the group consisting of glass fibers, carbon powder, calcium carbonate, cellulose powder, and cellulose fibers.

[0013] (Item 6) Use of rosin-based resins as modifiers for thermoplastic resins, as described in item 1.

[0014] (Item 7) The use described in item 6, wherein the thermoplastic resin further comprises a filler.

[0015] (Item 8) Use of the rosin resin described in item 1 for producing a resin composition containing a thermoplastic resin.

[0016] (Item 9) The use according to item 8, wherein the resin composition further comprises a filler. [Best Mode for Carrying Out the Invention]

[0017] Throughout this disclosure, the ranges of numerical values ​​such as physical properties and content may be set as appropriate (for example, by selecting from the values ​​listed in each item below). Specifically, if the examples of numerical value α are A3, A2, and A1 (A3 > A2 > A1), the range of numerical value α may include, for example, A3 or less, A2 or less, less than A3, less than A2, A1 or greater, A2 or greater, greater than A1, greater than A2, A1 to A2 (A1 or greater and A2 or less), A1 to A3, A2 to A3, A1 or greater and less than A3, A1 or greater and less than A2, A2 or greater and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less. In this disclosure, "~" is used to mean that the numerical values ​​listed before and after it are included as the lower and upper limits. The components and manufacturing methods of this disclosure will be described in detail below.

[0018] [Modifier for thermoplastic resins] This disclosure relates to a modifier for thermoplastic resins (hereinafter also referred to as the modifier), which includes a rosin-based resin (hereinafter also referred to as the rosin-based resin) having a mass residue rate (hereinafter also referred to as the mass residue rate) of 40% by mass or more after heating at 300°C for 2 hours, and a mixed methylcyclohexaneaniline cloud point (MMAP) (hereinafter also referred to as the MMAP) of -10 to 20°C.

[0019] By using the above-mentioned modifier for a thermoplastic resin, it functions (as a fluidity improver) so as to improve the fluidity during melting in the thermoplastic resin.

[0020] <Rosin-based resin> The above-mentioned rosin-based resin is not particularly limited as long as the mass residue ratio and MMAP are within the above ranges, and various known resins can be used. The above-mentioned rosin-based resin may be used alone or in combination of two or more.

[0021] The above-mentioned rosin-based resin includes, for example, rosin esters, rosin polyols, etc.

[0022] (Rosin esters) The above-mentioned rosin esters are not particularly limited, and various known ones can be used. The above-mentioned rosin esters include, for example, unmodified rosin esters, hydrogenated rosin esters, disproportionated rosin esters, polymerized rosin esters, α,β-unsaturated carboxylic acid-modified rosin esters, etc. The above-mentioned rosin esters may be used alone or in combination of two or more.

[0023] The unmodified rosin ester is obtained by reacting natural rosin, refined rosin (hereinafter, natural rosin and refined rosin are collectively also referred to as unmodified rosin) with alcohols.

[0024] The above-mentioned natural rosin includes, for example, natural rosin (gum rosin, tall oil rosin, wood rosin) derived from Pinus massoniana, Pinus elliottii, Pinus merkusii, Pinus caribaea, Pinus kesiya, Pinus taeda, Pinus palustris, etc.

[0025] The purified rosin described above can be obtained using various known methods. Specifically, it can be obtained using various known purification methods such as distillation, extraction, recrystallization, and adsorption. Distillation methods include, for example, distilling the natural rosin at a temperature of approximately 200-300°C and under reduced pressure of approximately 0.01-3 kPa. Extraction methods include, for example, making an alkaline aqueous solution of the natural rosin, extracting the insoluble unsaponifiable matter with various organic solvents, and then neutralizing the aqueous layer. Recrystallization methods include, for example, dissolving the natural rosin in an organic solvent as a good solvent, then distilling off the solvent to obtain a concentrated solution, and then adding an organic solvent as a poor solvent. 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 acetic acid esters such as ethyl acetate. Examples of poor solvents include n-hexane, n-heptane, cyclohexane, and isooctane. Adsorption methods include, for example, contacting a porous adsorbent with the above-mentioned natural rosin in a molten state or in a solution form dissolved in an organic solvent. Examples of porous adsorbents include activated carbon, metal oxides such as alumina, zirconia, silica, molecular sieves, zeolites, and porous clay with micropores.

[0026] Furthermore, the purified rosin may be subjected to the disproportionation and hydrogenation operations described later, either individually or in combination of two or more, as described below.

[0027] Furthermore, to improve the color tone, the purified rosin may be subjected to further dehydrogenation treatment. The dehydrogenation treatment is not particularly limited, and ordinary conditions can be used. For example, the dehydrogenation treatment is carried out in a sealed container in the presence of a dehydrogenation catalyst with the purified rosin at an initial hydrogen pressure of less than 10 kg / cm2, preferably less than 5 kg / cm2, and 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. Various known dehydrogenation catalysts can be used without particular limitations, but preferably palladium-based, rhodium-based, and platinum-based catalysts can be exemplified, and they are usually used supported on a carrier such as silica or carbon. The amount of 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 relative to the purified rosin.

[0028] The above alcohols are not particularly limited and include, for example, dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimergol, 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, from the viewpoint of high mass retention rate in the rosin-based resin, polyhydric alcohols having three or more hydroxyl groups are preferred, and more preferably glycerin, pentaerythritol, diglycerin, and dipentaerythritol are preferred. The above alcohols may be used individually or in combination of two or more.

[0029] 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, given their high mass retention rate in the rosin-based resin. In one embodiment, the dihydric alcohols are preferably bisphenol A and bisphenol F, for similar reasons.

[0030] The reaction conditions for the above-mentioned unmodified rosin and alcohols are not particularly limited, and various known reaction conditions can be used. For example, the reaction conditions for the above-mentioned unmodified rosin and alcohols can be carried out by adding an esterification catalyst as needed to the unmodified rosin and alcohols in the presence or absence of a solvent, at a temperature of about 250 to 280°C for about 1 to 8 hours.

[0031] Examples of the esterification catalysts include acid catalysts such as p-toluenesulfonic acid, acetic acid, methanesulfonic acid, hypophosphorous acid, and sulfuric acid; metal hydroxides such as calcium hydroxide and magnesium hydroxide; metal oxides such as calcium oxide and magnesium oxide; and metal salts such as iron chloride and calcium formate. One catalyst may be used alone, or two or more may be used in combination. Since water is produced as a result of the esterification reaction, the reaction can be carried out while removing the produced water from the system. Considering the color of the resulting unmodified rosin ester, it is desirable to carry out the reaction under an inert gas stream. The reaction may also be carried out under pressure if necessary.

[0032] Examples of the solvents mentioned above include hexane, cyclohexane, toluene, and xylene. If a solvent is used, the solvent or unreacted raw materials can be removed by vacuum distillation as needed.

[0033] In one embodiment, the amount of unmodified rosin and alcohols used is such that the ratio of OH groups of alcohols to COOH groups of unmodified rosin (equivalent ratio) is approximately 0.2 to 8, and from the perspective of having a high mass residue rate in the rosin-based resin, it is preferably approximately 0.8 to 8, and more preferably approximately 0.8 to 3.

[0034] Hydrogenated rosin esters are obtained by hydrogenating the unmodified rosin described above, and then further reacting the resulting hydrogenated rosin with alcohols to esterify it.

[0035] The above-mentioned hydrogenated rosin can be obtained using various known methods. Specifically, for example, the unmodified rosin can be heated and reacted (hydrogenated) under hydrogen pressure in the presence of a hydrogenation catalyst. Various known hydrogenation catalysts can be used, such as supported catalysts and metal powders. Examples of supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, and platinum-carbon, while examples of metal powders include nickel and platinum. In one embodiment, the amount of 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 raw material rosin. 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 to 300°C.

[0036] The above hydrogenation may be carried out with the unmodified rosin dissolved in a solvent, if necessary. The solvent used is not particularly limited, but any solvent that is inert to the reaction and readily dissolves the raw materials and products is acceptable. Specifically, for example, one or more of the following can be used: cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane, etc. The amount of solvent used is not particularly limited, but it is usually sufficient to use such a solvent that the solid content relative to the unmodified rosin is 10% by mass or more, preferably in the range of 10 to 70% by mass.

[0037] Furthermore, the hydrogenated rosin obtained may be subjected to the purification, hydrogenation, and disproportionation operations described later, either individually or in combination of two or more.

[0038] Furthermore, the above-mentioned dehydrogenation treatment may be performed on the above-mentioned hydrogenated rosin for the purpose of improving its color tone.

[0039] The reaction conditions for the above-mentioned hydrogenated rosin and alcohols are the same as those for the unmodified rosin ester. The alcohols used in the esterification of the hydrogenated rosin are also the same as those described above. Furthermore, the amounts of hydrogenated rosin and alcohols used are also the same as described above.

[0040] The order of the hydrogenation reaction and the esterification reaction is not limited to those described above; the hydrogenation reaction may be performed after the esterification reaction.

[0041] Disproportionated rosin esters are obtained by disproportionating the unmodified rosin described above, and then further reacting the disproportionated rosin with alcohols to esterify it.

[0042] The above-mentioned disproportionated rosin can be obtained using various known methods. Specifically, for example, the above-mentioned unmodified rosin can be heated in the presence of a disproportionation catalyst to react (disproportionate). Examples of disproportionation catalysts include various known ones such as 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 catalyst used is usually about 0.01 to 5 parts by mass, preferably about 0.01 to 1 part by mass, per 100 parts by mass of the raw material rosin. In one embodiment, the reaction temperature is about 100 to 300°C, preferably about 150 to 290°C.

[0043] Furthermore, the disproportionated rosin obtained may be subjected to the purification, hydrogenation, and disproportionation operations individually or in combination of two or more.

[0044] Furthermore, the above-mentioned dehydrogenation treatment may be performed on the disproportionate rosin in order to improve the color tone.

[0045] The reaction conditions for the disproportionated rosin and alcohols are the same as those for the unmodified rosin ester. The alcohols used in the esterification of the disproportionated rosin are also the same as those described above. Furthermore, the amounts of disproportionated rosin and alcohols used are also the same as described above.

[0046] The order of the disproportionation reaction and the esterification reaction is not limited to those described above; the disproportionation reaction may be performed after the esterification reaction.

[0047] Polymerized rosin esters are obtained by reacting polymerized rosin with alcohols. Polymerized rosin is a rosin derivative containing dimerized resin acid.

[0048] Known methods can be used to produce the polymerized rosin described above. Specifically, for example, one method involves reacting the unmodified rosin as a raw material 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.

[0049] Furthermore, the polymerized rosin used may be one which has been subjected to the above-mentioned purification, hydrogenation, disproportionation, and various treatments such as acrylication, maleation, and fumaration of α,β-unsaturated carboxylic acids, as described later. In addition, these various treatments may be performed individually or in combination of two or more.

[0050] 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 above. Furthermore, the polymerized rosin may be reacted with the unmodified rosin in combination with the alcohols.

[0051] The alcohols used in esterifying polymerized rosin are the same as described above.

[0052] The order of the polymerization reaction and the esterification reaction is not limited to those described above; the polymerization reaction may be carried out after the esterification reaction.

[0053] α,β-unsaturated carboxylic acid-modified rosin esters are obtained by reacting α,β-unsaturated carboxylic acid-modified rosin with alcohols.

[0054] The above-mentioned α,β-unsaturated carboxylic acid-modified rosin is obtained by adding an α,β-unsaturated carboxylic acid to the above-mentioned unmodified rosin, hydrogenated rosin, or disproportionated rosin.

[0055] The above α,β-unsaturated carboxylic acid is not particularly limited, and various known ones can be used. Specifically, examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, muconic anhydride, etc. In one embodiment, the above α,β-unsaturated carboxylic acid is preferably acrylic acid, maleic acid, maleic anhydride, or fumaric acid. In one embodiment, the amount of α,β-unsaturated carboxylic acid used is usually about 1 to 20 parts by mass, preferably about 1 to 3 parts by mass, per 100 parts by mass of the above unmodified rosin, from the viewpoint of excellent emulsification properties. The above α,β-unsaturated carboxylic acid may be used alone or in combination of two or more.

[0056] The method for producing the α,β-unsaturated carboxylic acid-modified rosin described above is not particularly limited, but for example, the α,β-unsaturated carboxylic acid is added to the unmodified or disproportionated rosin melted under heating, and the reaction is carried out at a temperature of about 180 to 240°C for about 1 to 9 hours. The above reaction may also be carried out while blowing an inert gas such as nitrogen into a sealed reaction system. Furthermore, in the above reaction, known catalysts such as Lewis acids such as zinc chloride, iron chloride, and tin chloride, or Brønsted acids such as p-toluenesulfonic acid and methanesulfonic acid may be used. The amount of these catalysts used is usually about 0.01 to 10% by mass relative to the unmodified rosin.

[0057] Furthermore, as the α,β-unsaturated carboxylic acid modified rosin mentioned above, a rosin that has been further subjected to the hydrogenation process described above may be used.

[0058] The reaction conditions between the α,β-unsaturated carboxylic acid-modified rosin and alcohols are not particularly limited, but for example, the reaction can be carried out by adding alcohol to α,β-unsaturated carboxylic acid-modified rosin that has been melted under heating, and reacting it at a temperature of about 250 to 280°C for about 15 to 20 hours. The above reaction may also be carried out while blowing an inert gas such as nitrogen into a sealed reaction system, and the aforementioned catalyst may be used.

[0059] The alcohols used in esterifying the α,β-unsaturated carboxylic acid-modified rosin are the same as described above. Furthermore, the amounts of the α,β-unsaturated carboxylic acid-modified rosin and alcohols used are also the same as described above.

[0060] Furthermore, the unmodified rosin ester, hydrogenated rosin ester, disproportionated rosin ester, polymerized rosin ester, and α,β-unsaturated carboxylic acid modified rosin ester may be those obtained by further treating the rosin esters with various processes such as purification, hydrogenation, disproportionation, and dehydrogenation. These treatments may be performed individually or in combination of two or more.

[0061] In one embodiment, the rosin esters are preferably selected from the group consisting of hydrogenated rosin esters and disproportionated rosin esters, given their high mass residue rate.

[0062] (Rosin polyol) Rosin polyols are reaction products of reactive components including rosins and epoxy resins.

[0063] The rosins mentioned above are not particularly limited, and various known types can be used. Examples of the rosins include unmodified rosin, hydrogenated rosin, disproportionated rosin, and the like.

[0064] The epoxy resins mentioned above are not particularly limited, and various known ones can be used. Examples of such epoxy resins 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, arylalkylene-type epoxy compounds, trihydroxybiphenyl triglycidyl ether, and 1,1,2,2-tetra(4-hydroxyphenyl)ethanetetraglycidyl ether.

[0065] Examples of the above-mentioned bisphenol-type epoxy resins include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol AD ​​type epoxy resin, tetrabromobisphenol A type epoxy resin, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl diglycidyl ether, and 2,2-bis(4-(β-hydroxypropoxy)phenyl)propane diglycidyl ether.

[0066] Examples of the above-mentioned novolac-type epoxy resins 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.

[0067] Examples of the above-mentioned 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.

[0068] Examples of the above-mentioned alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meth-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadienediepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, and 2,2-bis(4-hydroxycyclohexyl)propanediglycidyl ether.

[0069] Examples of the glycidylamine-type epoxy compounds mentioned above include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmethaminophenol, and tetraglycidylmetaxylylenediamine.

[0070] Examples of the glycidyl ester type epoxy compounds mentioned above include diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, and triglycidyl trimellitate.

[0071] The weight-average molecular weight (Mw) of the epoxy resin is not particularly limited. Examples of weight-average molecular weights of the epoxy resin include 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, and 2,500. 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 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, 10,000, etc. In one embodiment, the weight-average molecular weight of the epoxy resin is preferably 150 or higher, given the high mass retention rate of the rosin-based resin. The higher the weight-average molecular weight of the epoxy resin, the higher the mass retention rate tends to be. In one embodiment, the weight-average molecular weight of the epoxy resin is preferably about 150 to 10,000, and more preferably about 150 to 2,000, from the viewpoint of further improving the fluidity of the thermoplastic resin when it melts. The weight-average molecular weight is the polystyrene equivalent value obtained by gel permeation chromatography (GPC).

[0072] The epoxy equivalent (g / eq) of the epoxy resin mentioned above is not particularly affected. Examples of epoxy equivalents of the epoxy resin mentioned above include 100g / eq, 150g / eq, 180g / eq, 200g / eq, 300g / eq, 400g / eq, 500g / eq, 600g / eq, 700g / eq, 800g / eq, 900g / eq, 1,000g / eq, 1,100g / 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, and 2,500g / eq. Examples include 0g / eq, 2,600g / eq, 2,700g / eq, 2,800g / eq, 2,900g / eq, 3,000g / eq, 3,100g / eq, 3,200g / eq, 3,300g / eq, 3,400g / eq, 3,500g / eq, 3,600g / eq, 3,700g / eq, 3,800g / eq, 3,900g / eq, 4,000g / eq, 4,100g / eq, 4,200g / eq, 4,300g / eq, 4,400g / eq, 4,500g / eq, 4,600g / eq, 4,700g / eq, 4,800g / eq, 4,900g / eq, and 5,000g / eq. 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, from the viewpoint of a high mass residue rate of the rosin-based resin. The higher the epoxy equivalent of the epoxy resin, the higher the mass residue 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, from the viewpoint of further improving the fluidity of the thermoplastic resin when it melts.

[0073] The above-mentioned reaction components may include alcohols in addition to the rosins and epoxy resins. Examples of such 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, given the high mass retention rate of the rosin polyol.

[0074] The method for producing the above-mentioned rosin polyol is not particularly limited, and various known methods can be employed. Specifically, for example, one method involves carrying out a ring-opening addition reaction between the rosins and epoxy resin at 120 to 300°C under a nitrogen stream, with or without a catalyst.

[0075] Examples of the catalysts mentioned above include amine-based 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.

[0076] In the above ring-opening addition reaction, a solvent may be used as needed. The solvent is not particularly limited, but any solvent that is inert to the reaction and readily dissolves the starting materials and products is acceptable. Specifically, 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.

[0077] In one embodiment, the amount of rosins and epoxy resin used is typically such that one epoxy group in the epoxy resin corresponds to two OH groups, and the ratio of OH groups in the epoxy resin (total of epoxy groups and OH groups present in the epoxy resin) to COOH groups in the rosins (equivalent ratio) is approximately 0.8 to 22. However, given the high mass residue rate of the rosin-based resin, a ratio of approximately 0.8 to 10 is preferred.

[0078] In one embodiment, the rosin-based resin is preferably at least one selected from the group consisting of the rosin esters and the rosin polyols, in that it suppresses smoke generation during the melting of the thermoplastic resin and improves the fluidity during the melting of the thermoplastic resin, and more preferably the rosin esters, in that respect.

[0079] (Physical properties of rosin-based resins) The mass residual rate of the rosin resin is, for example, 100% by mass, 99% by mass, 98% by mass, 97% by mass, 96% by mass, 95% by mass, 94% by mass, 93% by mass, 92% by mass, 91% by mass, 90% by mass, 89% by mass, 88% by mass. %, 87% by mass, 86% by mass, 85% by mass, 84% by mass, 83% by mass, 82% by mass, 81% by mass, 80% by mass, 79% by mass, 78% by mass, 77% by mass, 76% by mass, 75% by mass, 74% by mass, 73% by mass, 72% by mass, 7 Examples include 1% by mass, 70% by mass, 69% by mass, 68% by mass, 67% by mass, 66% by mass, 65% by mass, 64% by mass, 63% by mass, 62% by mass, 61% by mass, 60% by mass, 59% by mass, 58% by mass, 57% by mass, 56% by mass, 55% by mass, 54% by mass, 53% by mass, 52% by mass, 51% by mass, 50% by mass, 49% by mass, 48% by mass, 47% by mass, 46% by mass, 45% by mass, 44% by mass, 43% by mass, 42% by mass, 41% by mass, 40% by mass, etc. In one embodiment, the mass residual rate of the rosin-based resin is preferably 40% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass, from the viewpoint of suppressing smoke generation when the thermoplastic resin melts. The higher the mass residue rate of the rosin-based resin, the more effectively smoke generation during the melting of the thermoplastic resin can be suppressed.

[0080] In this disclosure, the above-mentioned mass residue rate is measured by the method described in the examples below.

[0081] In the case of thermoplastic resins, particularly engineering plastics and super engineering plastics, the molding temperature is often 250°C or higher. The inventors hypothesized that when a modifier containing a rosin-based resin is used with a thermoplastic resin and smoke is emitted during melting, this is because the rosin-based resin contains many components that can volatilize and structures that can be thermally decomposed at the molding temperature, and the smoke is generated by these volatile components and thermal decomposition products. The inventors then evaluated the mass residue rate of rosin-based resins under harsh conditions of heating at a temperature equivalent to or higher than the molding temperature (300°C) for a long period of time (2 hours), and found that rosin-based resins with a mass residue rate of 40% or more have fewer such components and structures, and therefore smoke emission is suppressed even when used in the molding process of thermoplastic resins.

[0082] Furthermore, in the case of rosin-based resins, the details of components that can volatilize and structures that can be thermally decomposed at the molding temperature are diverse and difficult to specify. Therefore, the present inventors have identified rosin-based resins that can suppress smoke generation during the melting of thermoplastic resins by defining them by the above-mentioned mass residual rate.

[0083] Furthermore, in the above mass residual rate, if the heating temperature is lower than 300°C and / or the heating time is shorter than 2 hours, the heating conditions are mild, making it difficult to appropriately evaluate the tendency of smoke generation during the melting of thermoplastic resins in the case of rosin-based resins. In addition, when smoke is generated during the melting of thermoplastic resins, equipment and mold contamination occurs due to the smoke, but if the heating time is shorter than 2 hours, it is not possible to reflect the actual equipment and mold contamination during the molding process, making it difficult to appropriately evaluate the degree of contamination.

[0084] If the above-mentioned rosin-based resin has a mass residue rate of less than 40% by mass, when used in thermoplastic resins, it tends to generate a large amount of smoke during melting.

[0085] Examples of MMAPs for the above-mentioned rosin-based resins include 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, and -10°C. In one embodiment, the MMAP for the above-mentioned rosin-based resin is preferably -10 to 20°C, and more preferably -8 to 18°C, from the viewpoint of improving the fluidity of the thermoplastic resin when it melts.

[0086] In this disclosure, the above-mentioned MMAP is measured by the method described in the examples below.

[0087] When the MMAP of the above rosin-based resin is below -10°C, or above 20°C, the fluidity of the thermoplastic resin tends to decrease during melting.

[0088] The above-mentioned rosin-based resin is not particularly limited in terms of physical properties other than the mass residue rate and MMAP. Examples of the color tone of the above-mentioned 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, 5 Hazen, etc. In one embodiment, the color tone of the above-mentioned rosin-based resin is preferably around 10 to 400 Hazen, and more preferably around 10 to 200 Hazen, from the viewpoint of suppressing discoloration. In this disclosure, the color tones were measured in Hazen units in accordance with JIS K 0071-1 and in Gardner units in accordance with JIS K 0071-2.

[0089] The acid values ​​(mgKOH / g) of the above rosin-based resins are, for example, 200mgKOH / g, 195mgKOH / g, 190mgKOH / g, 185mgKOH / g, 180mgKOH / g, 175mgKOH / g, 170mgKOH / g, 165mgKOH / g, 160mgKOH / g, 155mgKOH / g, 150mgKOH / g, 145mgKOH / g, 140mgKOH / g, 135mgKOH / g, 130mgKOH / g, 125mgKOH / g, 120mgKOH / g, 115mgKOH / g, 110mgKOH / g, and 105mgKOH / g. mgKOH / 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 Examples include 13mgKOH / g, 12mgKOH / g, 11mgKOH / g, 10mgKOH / g, 9mgKOH / g, 8mgKOH / g, 7mgKOH / g, 6mgKOH / g, 5mgKOH / g, 4mgKOH / g, 3mgKOH / g, 2mgKOH / g, 1mgKOH / g, 0.9mgKOH / g, 0.8mgKOH / g, 0.7mgKOH / g, 0.6mgKOH / g, 0.5mgKOH / g, 0.4mgKOH / g, 0.3mgKOH / g, 0.2mgKOH / g, 0.1mgKOH / g, 0mgKOH / g, etc.In one embodiment, the acid value of the rosin-based 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, from the viewpoint of further suppressing smoke generation when the thermoplastic resin melts. In this disclosure, the acid value is the value measured according to JIS K0070.

[0090] The lower the acid value of the rosin-based resin, the more suppressed the decarboxylation of the rosin-based resin at high temperatures tends to be, and therefore the higher the mass residue rate tends to be. Similarly, the lower the number of moles of carboxyl groups (COOH) contained in the rosin-based resin, the higher the mass residue rate tends to be.

[0091] The higher the acid value of the rosin-based resin, the lower the MMAP tends to be. Also, the higher the number of moles of carboxyl groups (COOH) contained in the rosin-based resin, the lower the MMAP tends to be.

[0092] Examples of the weight-average molecular weights of the above rosin-based resins include 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, and 600. In one embodiment, the weight-average molecular weight of the rosin-based resin is preferably 600 or more, more preferably 700 or more, from the viewpoint of further suppressing smoke generation when the thermoplastic resin melts. In one embodiment, the weight-average molecular weight of the rosin-based 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 melts and further improving the fluidity when the thermoplastic resin melts. In this disclosure, the weight-average molecular weight is the polystyrene equivalent value obtained by gel permeation chromatography (GPC).

[0093] The higher the weight-average molecular weight of the rosin-based resin, the higher the mass residue rate tends to be. Also, the higher the weight-average molecular weight of the rosin-based resin, the higher the MMAP (mass residue rate), and the lower the weight-average molecular weight, the lower the MMAP tends to be.

[0094] In one embodiment, the rosin-based resin may optionally contain various known additives, provided that the effects of the present invention are not impaired. Examples of additives include dehydrating agents, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, and light stabilizers. These additives may be used individually or in combination of two or more.

[0095] (Additives) In one embodiment, the modifier may optionally include various known additives, as long as the effects of the present invention are not impaired. Examples of additives include dehydrating agents, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, and light stabilizers. The additives may be used individually or in combination of two or more. In one embodiment, the content of the additive is preferably 0.5 to 10 parts by mass per 100 parts by mass of the rosin-based resin.

[0096] (Use of modifiers for thermoplastic resins) The above-mentioned modifier can be used with various known thermoplastic resins. The thermoplastic resin may be used alone or in combination of two or more types. Examples of thermoplastic resins are those described below.

[0097] In one embodiment, the modifier is preferably used in a thermoplastic resin comprising at least one selected from the group consisting of polyamide, polycarbonate, polyphenylene ether, and polyolefin resin, from the viewpoint of further improving fluidity during melting, and more preferably in a thermoplastic resin comprising at least one selected from the group consisting of polyamide 66, polyamide 6, polycarbonate, modified polyphenylene ether resin, polyethylene, and polypropylene.

[0098] In one embodiment, the modifier contains the rosin-based resin and is therefore preferably used in thermoplastic resins with high molding temperatures, and more preferably in engineering plastics and super engineering plastics.

[0099] The amount of the above-mentioned modifier used is not particularly limited. Examples of the amount of the above-mentioned modifier used per 100 parts by mass of thermoplastic resin include 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. 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, from the standpoint of improving the fluidity of the thermoplastic resin when it melts, and preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin, from the standpoint of improving the fluidity of the thermoplastic resin when it melts and suppressing smoke generation when it melts. 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, from the standpoint of improving the fluidity of the thermoplastic resin when it melts and suppressing smoke generation when it melts.

[0100] Furthermore, when a filler described later is used in combination with the thermoplastic resin, the amount of the modifier used 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., per 100 parts by mass of 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, from the standpoint of improving the fluidity of the thermoplastic resin when it melts, and preferably 20 parts by mass or less per 100 parts by mass of the thermoplastic resin, from the standpoint of improving the fluidity of the thermoplastic resin when it melts and suppressing smoke generation when it melts. 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, more preferably about 0.5 to 15 parts by mass, and even more preferably about 5 to 10 parts by mass, from the standpoint of improving the fluidity of the thermoplastic resin when it melts and suppressing smoke generation when it melts.

[0101] Furthermore, when the above-mentioned modifier is used in a thermoplastic resin containing a filler, as described later, it can improve the mechanical properties of the molded article made 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 mechanical properties of the molded article by improving the interfacial adhesion between the thermoplastic resin and the filler.

[0102] The method of using the above-mentioned modifier is not particularly limited. For example, the modifier may be added to a mixer together with the thermoplastic resin and then melt-kneaded in the mixer. Examples of the above-mentioned mixer include a Banbury mixer, roll mixer, Brabender, single-screw extruder, twin-screw extruder, kneader, etc. The temperature of the melt-kneading is not particularly limited, but is usually in the range of -30°C to +30°C, which is the melting point of the thermoplastic resin.

[0103] [Resin composition] This disclosure relates to a resin composition comprising the above-mentioned modifier (or the above-mentioned rosin-based resin) and a thermoplastic resin.

[0104] <Thermoplastic resin> The thermoplastic resin described above is not particularly limited, and various known types can be used. The thermoplastic resin may be used individually or in combination of two or more types.

[0105] Examples of the thermoplastic resins mentioned above include polyolefin resins, styrene resins, ABS resins, polyamides, polyesters, polycarbonates, polyacetals, phenoxy resins, polymethyl methacrylate resins, polyphenylene ethers, polyphenylene sulfides, polyamide-imides, polyimides, polyetherimides, liquid crystal polymers, polyetherether ketones, polyethersulfones, polysulfones, polyarylates, fluororesins, and the like.

[0106] (Polyolefin resin) The above-mentioned polyolefin resin is not particularly limited, and various known resins can be used. The above-mentioned polyolefin resin may be used alone or in combination of two or more types.

[0107] Examples of the polyolefin resins mentioned above include homopolymers of α-olefins having approximately 2 to 8 carbon atoms, such as ethylene, propylene, and 1-butene; binary or ternary (co)polymers of the α-olefins; and binary or ternary (co)polymers of the α-olefins with α-olefins having approximately 9 to 18 carbon atoms, conjugated dienes, unconjugated dienes, unsaturated carboxylic acids, (meth)acrylic acid esters, and vinyl acetate, etc.

[0108] Examples of the above α-olefins having approximately 2 to 18 carbon atoms include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, and 1-octadecene. Examples of the above conjugated and unconjugated dienes include butadiene, isoprene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene. Examples of the above 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. Furthermore, the above unsaturated carboxylic acids may be neutralized with a base or the like. Examples of the above (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, and isooctyl (meth)acrylate. Two or more of these α-olefins, conjugated dienes, unconjugated dienes, unsaturated carboxylic acids, and (meth)acrylic acid esters may be used.

[0109] Examples of the polyolefin resins mentioned above include 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.

[0110] (Styrene resin) The styrene-based resins mentioned above are not particularly limited, and various known resins can be used. The styrene-based resins may be used individually or in combination of two or more types.

[0111] Examples of the above-mentioned styrene-based resins include resins obtained by polymerizing a styrene-based compound with other compounds copolymerizable thereto, in the presence or absence of a rubbery polymer. Examples of the above-mentioned styrene-based compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromstyrene, dibromstyrene, fluorostyrene, and tribromstyrene. Examples of other compounds copolymerizable with the above-mentioned styrene-based compounds 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. Examples of the above-mentioned rubbery polymers include polybutadiene, polyisoprene, diene copolymers, copolymers of ethylene and α-olefins, copolymers of ethylene and unsaturated carboxylic acid esters, non-conjugated diene polymers of ethylene and propylene, and acrylic rubber. The styrene-based compound, other compounds copolymerizable with the styrene-based compound, and the rubbery polymer may be used individually or in combination of two or more. In one embodiment, the styrene-based resin is preferably polystyrene.

[0112] (polyamide) The polyamides mentioned above are not particularly limited, and various known types can be used. The polyamides may be used individually or in combination of two or more types.

[0113] The above-mentioned polyamide is a resin made of a polymer having amide bonds, and is mainly derived from amino acids, lactams, or diamines and dicarboxylic acids. The above-mentioned polyamide can be used as polyamide homopolymers or copolymers derived from these raw materials, either individually or in mixtures. Furthermore, two or more of these raw materials may be used in combination.

[0114] Examples of the above amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid.

[0115] Examples of the lactams mentioned above include ε-caprolactam and ω-laurolactam.

[0116] Examples of the above-mentioned diamines include aliphatic diamines, aromatic diamines, and alicyclic diamines. Examples of aliphatic diamines include tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, and 5-methylnonamethylenediamine. Examples of aromatic diamines include metaxylylenediamine and paraxylylenediamine. 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.

[0117] Examples of the above-mentioned dicarboxylic acids include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids. Examples of aliphatic dicarboxylic acids include adipic acid, superiric acid, azelaic acid, sebacic acid, and dodecanedioic acid. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. Examples of alicyclic dicarboxylic acids include hexahydroterephthalic acid and hexahydroisophthalic acid.

[0118] The above polyamide resins include, for example, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebaamide (polyamide 610), polypentamethylene sebaamide (polyamide 510), polyhexamethylene dodecamide (polyamide 612), polyundecaneamide (polyamide 11), and Lidodecanamide (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 / Po Polyhexamethylene isophthalamide / polycaproamide copolymer (Polyamide 66 / 6I / 6), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (Polyamide 6T / 6I), polyhexamethylene terephthalamide / polydodecaneamide copolymer (Polyamide 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (Po Examples include 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.

[0119] In one embodiment, the polyamides are preferably polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 9T, polyamide 6 / 66 copolymer, and polyamide 6 / 12 copolymer. Similarly, more preferably polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, and polyamide 9T are included.

[0120] (polyester) The above-mentioned polyester is not particularly limited, and various known types can be used. The above-mentioned polyester may be used alone or in combination of two or more types.

[0121] The above-mentioned polyesters include polymers or copolymers obtained by a condensation reaction mainly consisting of a polycarboxylic acid (or its ester-forming derivative) and a polyhydric alcohol (or its ester-forming derivative), or mixtures thereof. In addition, two or more types of polycarboxylic acids and polyhydric alcohols may be used in combination.

[0122] Examples of the polycarboxylic acids mentioned above include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, tricarboxylic acids, and their ester-forming derivatives. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4'-diphenyl etherdicarboxylic acid, and 5-sodium sulfisoisophthalic acid. Examples of aliphatic dicarboxylic acids include adipic acid, sebacic acid, azelaic acid, and dodecanedionic acid. Examples of alicyclic dicarboxylic acids include 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples of tricarboxylic acids include trimellitic acid.

[0123] Examples of the polyhydric alcohols mentioned above include aliphatic glycols, alicyclic diols, aromatic diols, trimethylolpropane, pentaerythritol, glycerol, and ester-forming derivatives thereof. Examples of the aliphatic glycols include 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. Examples of the alicyclic diols include cyclopentanediol, cyclohexanediol, and hydrogenated bisphenol A. Examples of the aromatic diols include bisphenol A ethylene oxide (1 mol to 100 mol) adducts, bisphenol A propylene oxide (1 mol to 100 mol) adducts, and xylene glycol.

[0124] Examples of the above-mentioned polyesters 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.

[0125] 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, and more preferably polyethylene terephthalate or polybutylene terephthalate.

[0126] (Polycarbonate) The polycarbonate mentioned above is not particularly limited, and various known types can be used. The polycarbonate may be used individually or in combination of two or more types.

[0127] The above-mentioned polycarbonate can be obtained, for example, by reacting an aromatic dihydroxy compound with a carbonate precursor. Furthermore, the above-mentioned polycarbonate may have a linear structure or a branched structure.

[0128] Examples of the above-mentioned aromatic dihydroxy compounds include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxydiaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, hydroquinones, resorcinol, 4,4'-dihydroxydiphenyl, and 4,4'-dihydroxybenzophenone. These aromatic dihydroxy compounds may be used individually or in combination of two or more.

[0129] The above bis(hydroxyaryl)alkanes include, for example, 2,2-bis(4-hydroxyphenyl)propane (so-called 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, Examples include 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, and bis(4-hydroxyphenyl)diphenylmethane.

[0130] Examples of the above-mentioned bis(hydroxyaryl)cycloalkanes include 1,1-bis(4-hydroxyphenyl)cyclohexane (so-called 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.

[0131] Examples of the above-mentioned dihydroxydiaryl ethers include 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether. Examples of the above-mentioned dihydroxydiaryl sulfides include 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide. Examples of the above-mentioned dihydroxydiaryl sulfoxides include 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide. Examples of the above-mentioned dihydroxydiaryl sulfones include 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.

[0132] Examples of the carbonate precursors mentioned above include carbonyl halides and diester carbonates. These carbonate precursors may be used individually or in combination of two or more.

[0133] Examples of the carbonyl halides mentioned above include phosgene; bischloroformates of dihydroxy compounds, monochloroformates of dihydroxy compounds, and other haloformates. The carbonyl halides may be used individually or in combination of two or more.

[0134] Examples of the above-mentioned dicarbonate diesters include diaryl carbonates such as diphenyl carbonate, ditrile 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; and carbonates of dihydroxy compounds such as biscarbonate and cyclic carbonates of dihydroxy compounds. The dicarbonate diester may be used alone or in combination of two or more types.

[0135] Examples of methods for producing the polycarbonate mentioned above include interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0136] Furthermore, the polycarbonate may be a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid, a copolymerized polycarbonate resin copolymerized with a difunctional alcohol (including alicyclic), or a polyester carbonate resin copolymerized with both such difunctional carboxylic acid and difunctional alcohol. Two or more of these polycarbonates may be used.

[0137] (Polyphenylene ether) The polyphenylene ethers mentioned above are not particularly limited, and various known types can be used. One type of polyphenylene ether may be used alone, or two or more types may be used in combination.

[0138] Examples of the polyphenylene ethers mentioned above include homopolymers or copolymers consisting of repeating units represented by the following general formula (1).

[0139] [ka] (In formula (1), R1, R2, R3, and R4 are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted aryl group, and n is the number of repetitions.)

[0140] Examples of homopolymers 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, and poly(2,6-dichloro-1,4-phenylene) ether.

[0141] Examples of copolymers include copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymers of 2,6-dimethylphenol and o-cresol, and copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol.

[0142] The above-mentioned method for producing polyphenylene ether is not particularly limited and can be obtained using various known means. Specifically, examples include the production methods described in U.S. Patent No. 3,306874, No. 3,306875, No. 3,257357, No. 3,257358, Japanese Patent Publication No. 50-51197, Japanese Patent Publication No. 52-17880, and Japanese Patent Publication No. 63-152628, etc.

[0143] The above-mentioned polyphenylene ether may contain various other phenylene ether units as partial structures, to the extent that it does not impair the effects 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. Furthermore, the polyphenylene ether resin may also have a small amount of diphenoquinone or the like bonded to its main chain. Furthermore, the polyphenylene ether resin may be modified with maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and their acid anhydrides, etc., or in which one or two of the two carboxyl groups of these unsaturated dicarboxylic acids are esterified, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, styrene, epoxidized natural oils, etc., unsaturated alcohols with the general formula CnH2n-3OH (where n is a positive integer) such as allyl alcohol, 4-penten-1-ol, 1,4-pentadiene-3-ol, etc., unsaturated alcohols with the general formula CnH2n-5OH, CnH2n-7OH (where n is a positive integer), etc. These modified polyphenylene ether resins may be used individually or in combination of two or more types. Furthermore, the melting point of the modified polyphenylene ether resin is defined as the peak top temperature of the peak observed in the temperature-heat flow graph obtained when the temperature is increased at 20°C / min using a differential thermal scanning calorimeter (DSC). If there are multiple peak top temperatures, the highest of them is used.

[0144] The above-mentioned 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 copolymer, styrene-butadiene copolymer, and acrylonitrile-styrene copolymer.

[0145] In one embodiment, when the polyphenylene ether is a mixture containing polyphenylene ether and polystyrene (a so-called modified polyphenylene ether resin), the polyphenylene ether content is typically 70% by mass or more, preferably 80% by mass or more, relative to the total amount of polyphenylene ether and polystyrene.

[0146] Examples of commercially available modified polyphenylene ether resins include "Yupiace" (registered trademark) manufactured by Mitsubishi Engineering Plastics Corporation, "NORYL" (registered trademark) manufactured by SABIC Corporation, and "Zylon" (registered trademark) manufactured by Asahi Kasei Corporation.

[0147] (Polyphenylene sulfide) The polyphenylene sulfide mentioned above is not particularly limited, and various known types can be used. The polycarbonate may be used alone or in combination of two or more types.

[0148] The above-mentioned polyphenylene sulfides can be obtained, for example, by reacting a polyhalogen aromatic compound with a sulfidating agent in a polar organic solvent.

[0149] Examples of the polyhalogen aromatic compounds mentioned above include 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, and 1-methoxy-2,5-dichlorobenzene, with p-dichlorobenzene being preferred. It is also possible to combine two or more different polyhalogen aromatic compounds to form copolymers, but it is preferable to use a p-dihalogen aromatic compound as the main component.

[0150] Examples of the sulfidating agents include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide. Examples of 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 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 anhydrous form. The sulfidating agents may be used individually or in combination of two or more.

[0151] Furthermore, the above-mentioned sulfidizing agent may also be an alkali metal sulfide prepared from an alkali metal hydroxide 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.

[0152] Furthermore, alkali metal hydroxides and / or alkaline earth metal hydroxides can be used in combination with the above-mentioned sulfidizing agent. In one embodiment, the alkali metal hydroxides are preferably sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures of two or more of these, and the alkaline earth metal hydroxides are, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, and sodium hydroxide, which is preferred.

[0153] The above-mentioned polyphenylene sulfide can be produced in high yield by recovery and post-treatment. Specifically, it can be produced by methods such as those described in Japanese Patent Publication No. 45-3368 for obtaining polymers with relatively small molecular weights, or by methods described in Japanese Patent Publication No. 52-12240 and Japanese Patent Application Publication No. 61-7332 for obtaining polymers with relatively large molecular weights. The polyphenylene sulfide resin obtained by the above methods can also be used after undergoing various treatments such as crosslinking / increasing molecular weight by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvents, hot water, or acidic aqueous solutions, and activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates, and functional group-containing disulfide compounds.

[0154] Examples of commercially available polyphenylene sulfide include "Torelina" (registered trademark) from Toray Industries, Inc., "DIC.PPS" (registered trademark) from DIC Corporation, and "Durafide" (registered trademark) from Polyplastics Co., Ltd.

[0155] (Liquid crystal polymer) The above-mentioned liquid crystal polymer is not particularly limited, and various known types can be used. The liquid crystal polymer may be used alone or in combination of two or more types.

[0156] Examples of the above-mentioned liquid crystal polymers include liquid crystal polyesters and liquid crystal polyesteramides. Liquid crystal polyesters are not particularly limited, but examples include aromatic polyesters. In one embodiment, the liquid crystal polyester is preferably a fully aromatic polyester made using only aromatic compounds as raw material monomers. Liquid crystal polyesteramides are not particularly limited, but examples include aromatic polyesteramides. In one embodiment, the liquid crystal polyesteramide is preferably a fully aromatic polyesteramide made using only aromatic compounds as raw material monomers. Furthermore, as the above-mentioned liquid crystal polymer, polyesters partially containing aromatic polyesters or aromatic polyesteramides within the same molecular chain can also be used.

[0157] The above aromatic polyesters are not particularly limited, but for example, (1) Polyesters consisting mainly of one or more aromatic hydroxycarboxylic acids and their derivatives; (2) Primarily (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) Polyesters comprising one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof; (3) Primarily (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives, (c) Polyesters comprising one or more aromatic diols, alicyclic diols, aliphatic diols, and their derivatives.

[0158] The above aromatic polyesteramides are not particularly limited, but for example, (1) Primarily (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) one or more aromatic hydroxyamines, aromatic diamines, and their derivatives, (c) Polyesteramides comprising one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives; (2) Primarily (a) one or more aromatic hydroxycarboxylic acids and their derivatives, (b) one or more aromatic hydroxyamines, aromatic diamines, and their derivatives, (c) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives, (d) Examples include polyester amides comprising one or more aromatic diols, alicyclic diols, aliphatic diols, and their derivatives. Furthermore, molecular weight modifiers may be used in combination with the above components as needed.

[0159] The above aromatic hydroxycarboxylic acids include, for example, aromatic hydroxycarboxylic acids such as 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- Examples include alkyl, alkoxy, or halogen-substituted aromatic hydroxycarboxylic acids such as 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.

[0160] Examples of the above aromatic diols include 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, or alkyl, alkoxy, or halogen-substituted aromatic diols such as chlorohydroquinone, methylhydroquinone, tert-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcinol, and 4-methylresorcinol.

[0161] Examples of the above aromatic dicarboxylic acids include 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, diphenyl ether-4,4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenoxyethane-3,3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, and 1,6-naphthalenedicarboxylic acid, or 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.

[0162] Examples of the above-mentioned aromatic hydroxyamines 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 above aromatic diamines 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).

[0163] 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 polyesteramide is more preferably an aromatic polyesteramide having the aromatic hydroxycarboxylic acid as a constituent component.

[0164] The method for producing the above-mentioned liquid crystal polymer is not particularly limited and can be obtained using various known means. Specifically, for example, it can be produced by known methods using the above-mentioned raw material monomer compound (or mixture of raw material monomers) and direct polymerization or transesterification. However, usually, melt polymerization, solution polymerization, slurry polymerization, solid-phase polymerization, etc., or a combination of two or more of these is used, with melt polymerization or a combination of melt polymerization and solid-phase polymerization being preferred. If the compound has ester-forming ability, it may be used in polymerization as is, or it may be used in which the precursor has been modified into a derivative having ester-forming ability using an acylating agent or the like in the step before polymerization. Examples of acylating agents include carboxylic acids such as acetic anhydride.

[0165] Various catalysts may be used in the polymerization described above. 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), as well as organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The amount of catalyst used is usually about 0.001 to 1% by mass relative to the total mass of the monomer, and is particularly preferably about 0.01 to 0.2% by mass.

[0166] In one embodiment, the liquid crystal polymer is preferably a liquid crystal polyester, which has excellent heat resistance and high strength in the resin composition, and more preferably a fully aromatic polyester, which also has excellent heat resistance and high strength.

[0167] In one embodiment, the thermoplastic resin in the above resin composition preferably includes at least one selected from the group consisting of polyamide, polycarbonate, polyphenylene ether, and polyolefin resin, from the viewpoint of excellent fluidity when the resin composition is melted, 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.

[0168] Even when the molding temperature is high, for example, when engineering plastics or super engineering plastics are used as the thermoplastic resin, the above-mentioned resin composition contains the above-mentioned modifier, which suppresses smoke generation during melting and exhibits excellent fluidity during melting.

[0169] (Filler) In one embodiment, the resin composition may optionally include a filler. The filler is not particularly limited, and various known fillers may be used. The filler may be used alone or in combination of two or more types.

[0170] Examples of the filler's shape include spherical, needle-shaped, fibrous, and plate-shaped.

[0171] Examples of the above fillers include 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, flaky carbon, and carbon nanotubes. Specific examples of metals that make up metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

[0172] The above fibers are not particularly limited and various known fibers can be used. Examples of the above fibers include glass fibers; alumina fibers; polyester fibers, polyamide fibers, polyimide fibers, polyvinyl alcohol modified fibers, polyvinyl chloride fibers, polyolefin (polyethylene, polypropylene) fibers, fluororesin fibers, polybenzimidazole fibers, acrylic fibers, phenol fibers, polyamide fibers, aramid fibers, cellulose (nano) fibers, liquid crystal polymer (liquid crystal polyester, liquid crystal polyesteramide) fibers, polyetherketone fibers, polyethersulfone fibers, polyphenylene ether fibers, polyphenylene sulfide fibers, and other organic fibers; and metal fibers made of metals such as iron, gold, silver, copper, aluminum, brass, and stainless steel. The above fibers may be used individually or in combination of two or more types.

[0173] In one embodiment, the fibers preferably include at least one selected from the group consisting of glass fibers and organic fibers, and more preferably include at least one selected from the group consisting of glass fibers and cellulose fibers.

[0174] In one embodiment, the filler preferably includes at least one selected from the group consisting of glass fibers, carbon powder, calcium carbonate, cellulose powder, and cellulose fibers, from the viewpoint of excellent mechanical properties of the resin composition.

[0175] Conventionally, in resin compositions containing the above-mentioned filler, the melt viscosity of the resin composition becomes very high due to the filler, which can result in extremely poor moldability. However, the resin composition of this disclosure, by using the above-mentioned modifier, has a lower melt viscosity even when it contains the above-mentioned filler, and therefore exhibits excellent moldability.

[0176] Furthermore, when the resin composition contains the filler, using the modifier improves the mechanical properties of the molded article 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 article.

[0177] (Additives) In one embodiment, the resin composition may optionally contain additives, provided that they do not impair the effects of the present invention. Examples of additives include flame retardants, conductivity imparters, nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insecticides, deodorants, color inhibitors, heat stabilizers, mold release agents, antistatic agents, plasticizers, colorants, dyes, foaming agents, antifoaming agents, coupling agents, inorganic pigments, organic pigments, fluidity improvers other than the rosin-based resins, light stabilizers, and the like.

[0178] (Content of each component) If the above resin composition does not contain the above filler, the content of the above modifier in the above resin composition is not particularly limited. Examples of the content of the above modifier in the above resin composition include 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., per 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 per 100 parts by mass of thermoplastic resin, from the viewpoint of superior fluidity when the resin composition is melted, and preferably 20 parts by mass or less per 100 parts by mass of thermoplastic resin, from the viewpoint of superior fluidity when the resin composition is melted and further suppression of smoke generation when the resin composition is melted. In one embodiment, the content of the modifier in the resin composition 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, from the viewpoint of superior fluidity when the resin composition is melted and further suppression of smoke generation when the resin composition is melted.

[0179] When the above resin composition contains the above filler, the content of the above modifier in the above resin composition is not particularly limited. Examples of the content of the above modifier in the above resin composition include 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., per 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 thermoplastic resin, from the viewpoint of superior fluidity when the resin composition is melted, and preferably 20 parts by mass or less per 100 parts by mass of thermoplastic resin, from the viewpoint of superior fluidity when the resin composition is melted and further suppression of smoke generation when the resin composition is melted. In one embodiment, the content of the modifier 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, from the viewpoint of superior fluidity when the resin composition is melted and further suppression of smoke generation when the resin composition is melted.

[0180] When the above resin composition does not contain the above filler, the content of the above rosin-based resin in the above resin composition is not particularly limited. Examples of the content of the above rosin-based resin in the above resin composition include 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., per 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 thermoplastic resin, from the viewpoint of superior fluidity when the resin composition is melted, and preferably 20 parts by mass or less per 100 parts by mass of thermoplastic resin, from the viewpoint of superior fluidity when the resin composition is melted and further suppression of 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, more preferably about 0.1 to 10 parts by mass, and even more preferably about 0.5 to 5 parts by mass, from the viewpoint of superior fluidity when the resin composition is melted and further suppression of smoke generation when the resin composition is melted.

[0181] When the above resin composition contains the above filler, the content of the above rosin-based resin in the above resin composition is not particularly limited. Examples of the content of the above rosin-based resin in the above resin composition include 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., per 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 thermoplastic resin, from the viewpoint of superior fluidity when the resin composition is melted, and preferably 20 parts by mass or less per 100 parts by mass of thermoplastic resin, from the viewpoint of superior fluidity when the resin composition is melted and further suppression of 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, more preferably about 0.5 to 15 parts by mass, and even more preferably about 2 to 10 parts by mass, from the viewpoint of superior fluidity when the resin composition is melted and further suppression of smoke generation when the resin composition is melted.

[0182] When the above resin composition contains the above filler, the amount of filler in the resin composition is not particularly limited. Examples of the amount of filler in the above resin composition include 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., per 100 parts by mass of thermoplastic resin. In one embodiment, the amount of filler in the above resin composition is preferably 150 parts by mass or less, and more preferably 120 parts by mass or less, per 100 parts by mass of thermoplastic resin, from the viewpoint of superior fluidity when the resin composition is melted.

[0183] The content of the additive in the above resin composition is not particularly limited. Examples of the content of the additive in the above resin composition include 100 parts by mass, 95 parts by mass, 90 parts by mass, 85 parts by mass, 80 parts by mass, 75 parts by mass, 70 parts by mass, 65 parts by mass, 60 parts by mass, 55 parts by mass, 50 parts by mass, 45 parts by mass, 40 parts by mass, 35 parts by mass, 30 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, 10 parts by mass, 5 parts by mass, 1 part by mass, 0.5 parts by mass, 0.1 parts by mass, 0.05 parts by mass, 0.01 parts by mass, 0.005 parts by mass, 0.001 parts by mass, etc., per 100 parts by mass of the above resin composition. In one embodiment, the content of the additive in the above resin composition is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more, per 100 parts by mass of the above resin composition. In one embodiment, the content of the additive in the resin composition is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less, per 100 parts by mass of the resin composition.

[0184] (Method for manufacturing resin compositions) The method for producing the above resin composition is not particularly limited, and various known methods can be employed. For example, one method for producing the above resin composition is to pre-mix the above modifier (or the above rosin-based resin), the above thermoplastic resin, and optionally the above filler and the above additive using various mixers such as a tumbler mixer or a Henschel mixer, and then melt-knead the mixture using a mixer such as a Banbury mixer, roll mixer, Brabender, single-screw extruder, twin-screw extruder, or kneader. The temperature of the melt-kneading is not particularly limited, but is usually in the range of -30°C to +30°C, which is the melting point of the above thermoplastic resin.

[0185] In the production of the above resin composition, using the above modifier or the above rosin-based resin increases the fluidity of the resin composition during melt-kneading, resulting in excellent productivity. Furthermore, conventionally, in the production of resin compositions containing fillers, the melt viscosity of the resin composition becomes very high due to the fillers, resulting in an extreme decrease in fluidity during melt-kneading. However, by using the above modifier or the above rosin-based resin, the fluidity during melt-kneading is increased even in the production of resin compositions containing fillers.

[0186] Furthermore, in the production of the above resin composition, even when the above modifier or the above rosin-based resin is used, smoke generation during melt kneading is suppressed.

[0187] [Molded body] The molded articles of this disclosure are obtained by molding the above-mentioned resin composition by various known molding methods. There are no particular restrictions on the shape of the molded article, and it can be appropriately selected according to the application and purpose of the molded article. Examples include plate-shaped, rod-shaped, sheet-shaped, film-shaped, cylindrical, annular, circular, elliptical, polygonal, irregularly shaped, hollow, frame-shaped, box-shaped, and panel-shaped articles.

[0188] The method for forming the above-mentioned molded article is not particularly limited, and conventionally known molding methods can be employed. Specifically, examples include injection molding, injection compression molding, extrusion molding, stretch film molding, inflation molding, shape extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating) molding, press molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding. Among these, molding is preferably carried out by injection molding. Examples of injection molding machines include known injection molding machines such as ultra-high-speed injection molding machines and injection compression molding machines.

[0189] The above-mentioned molded products can be used for a variety of applications, including automotive parts, electrical and electronic components, building materials, various containers, daily necessities, household goods, and hygiene products.

[0190] [Use as a modifier for thermoplastic resins] The above-mentioned rosin-based resin can be used as a modifier for thermoplastic resins. When the above-mentioned rosin-based resin is used in a thermoplastic resin, the fluidity of the thermoplastic resin during melting is improved. The thermoplastic resin is not particularly limited, and examples include those mentioned above.

[0191] 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 resin, in order to further improve fluidity during melting, and more preferably 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.

[0192] In one embodiment, the rosin-based resin is preferably used as a modifier for thermoplastic resins with high molding temperatures, and more preferably for engineering plastics and super engineering plastics.

[0193] The amount of the rosin-based resin used as a modifier for thermoplastic resins is not particularly limited. The amount of the rosin-based resin used may be, for example, the amount of the modifier described above.

[0194] Furthermore, when the above-mentioned rosin-based resin is used as a modifier for thermoplastic resins containing fillers, it can improve the mechanical properties of the molded article compared to cases where the above-mentioned rosin-based resin is not used. Although the details are unclear, it is presumed that the above-mentioned rosin-based resin improves the mechanical properties of the molded article by improving the interfacial adhesion between the thermoplastic resin and the filler.

[0195] This disclosure provides the following items: (Item A1) The mass residue rate after heating at 300°C for 2 hours is 40% by mass or more. The mixed methylcyclohexaneaniline cloud point (MMAP) is -10 to 20°C. Contains rosin-based resins, A modifier for thermoplastic resins. (Item A2) A modifier for thermoplastic resins as described above, wherein the rosin-based resin is at least one selected from the group consisting of rosin esters and rosin polyols. (Item A3) The modifier for thermoplastic resins as described above, wherein the rosin esters are rosin esters derived from polyhydric alcohols having three or more hydroxyl groups. (Item A4) A modifier for thermoplastic resins according to any of the above items, wherein the rosin esters are at least one selected from the group consisting of hydrogenated rosin esters and disproportionated rosin esters. (Item A5) A modifier for any of the above-mentioned thermoplastic resins, wherein the rosin polyol is a rosin polyol made from epoxy resin having a weight-average molecular weight of 150 to 2,000. (Item A6) A modifier for thermoplastic resins of any of the above items, wherein the mass residue rate of the rosin-based resin after heating at 300°C for 2 hours is 70% by mass or more. (Item A7) A modifier for any of the above-mentioned thermoplastic resins, wherein the mixed methylcyclohexaneaniline cloud point (MMAP) of the rosin-based resin is -8 to 18°C. (Item A8) A modifier for any of the above-mentioned thermoplastic resins, wherein the rosin-based resin has a color tone of 10 to 200 Hazen. (Item A9) A modifier for any of the above-mentioned thermoplastic resins, wherein the acid value of the rosin-based resin is 200 mg KOH / g or less. (Item A10) A modifier for any of the above-mentioned thermoplastic resins, wherein the acid value of the rosin-based resin is 50 mg KOH / g or less. (Item A11) A modifier for any of the above-mentioned thermoplastic resins, wherein the acid value of the rosin-based resin is 20 mg KOH / g or less. (Item A12) A modifier for any of the above-mentioned thermoplastic resins, wherein the acid value of the rosin-based resin is 15 mg KOH / g or less. (Item A13) A modifier for any of the above-mentioned thermoplastic resins, wherein the acid value of the rosin-based resin is 10 mg KOH / g or less. (Item A14) A modifier for any of the above-mentioned thermoplastic resins, wherein the acid value of the rosin-based resin is 0.1 mg KOH / g or less. (Item A15) A modifier for any of the above-mentioned thermoplastic resins, wherein the weight-average molecular weight of the rosin-based resin is 600 to 4,000. (Item A16) A modifier for any of the above-mentioned thermoplastic resins, wherein the weight-average molecular weight of the rosin-based resin is 600 to 3,000. (Item A17) A modifier for any of the above-mentioned thermoplastic resins, wherein the weight-average molecular weight of the rosin-based resin is 600 to 2,500. (Item A18) A modifier for any of the above-mentioned thermoplastic resins, wherein the weight-average molecular weight of the rosin-based resin is 700 to 2,500. (Item A19) A resin composition comprising any of the above-mentioned modifiers and a thermoplastic resin. (Item A20) The resin composition of 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) Furthermore, a resin composition comprising any of the above items, including 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 fibers, carbon powder, calcium carbonate, cellulose powder, and cellulose fibers. (Item A23) A resin composition according to any of the above items, wherein the content of the modifier is 0.1 to 10 parts by mass per 100 parts by mass of thermoplastic resin. (Item A24) A resin composition according to any of the above items, wherein 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 of the resin compositions listed above. (Item A26) The use of any of the above-mentioned rosin-based resins as a modifier for thermoplastic resins. (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 resins. (Item A28) The use of item A26 or item A27, wherein the thermoplastic resin further contains a filler. (Item A29) The use of item A28, wherein the filler comprises at least one selected from the group consisting of glass fibers, carbon powder, calcium carbonate, cellulose powder, and cellulose fibers. (Item A30) The use of any of the above items A26 to A29, wherein the amount of 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 rosin-based resin used is 0.5 to 15 parts by mass per 100 parts by mass of thermoplastic resin, and the content of the filler is 120 parts by mass or less per 100 parts by mass of thermoplastic resin. (Item A32) The use of any of the above-mentioned rosin-based resins for manufacturing 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 resins. (Item A34) The use of item A32 or item A33, wherein the resin composition further contains a filler. (Item A35) The use of item A34, wherein the filler comprises at least one selected from the group consisting of glass fibers, carbon powder, calcium carbonate, cellulose powder, and cellulose fibers. (Item A36) The use of any of the above items A32 to A35, wherein the amount of 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 rosin-based resin used is 0.5 to 15 parts by mass per 100 parts by mass of thermoplastic resin, and the content of the filler is 120 parts by mass or less per 100 parts by mass of thermoplastic resin.

[0196] The modifier for thermoplastic resins provided in this disclosure can improve the fluidity during melting and thus the moldability of thermoplastic resins when used in such applications. Furthermore, the modifier can suppress smoke generation during melting even when used in thermoplastic resins. [Examples]

[0197] The present invention will be described in more detail below with reference to examples of the present invention, but the present invention is actually... This is not limited to the examples provided. Note that "part" and "%" in the examples refer to, respectively... This represents "parts by mass" and "mass %".

[0198] <Manufacturing of rosin-based resins> Manufacturing Example 1 In a reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and vacuum device, 1000 parts of Chinese gum rosin (acid value 170.0 mg KOH / g, softening point 74°C, color 7 Gardner) and 0.3 parts of palladium carbon (palladium loading 5%, water content 50%) as catalyst were charged. Under a nitrogen seal, the mixture was stirred at 275°C for 5 hours to carry out a disproportionation reaction, yielding disproportionated rosin with an acid value of 155.0 mg KOH / g and a color of 7 Gardner. Next, the disproportionated rosin was distilled under a nitrogen seal under a reduced pressure of 5 mmHg, and the resulting main distillate was used as purified disproportionated rosin.

[0199] In a reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and vacuum device, 500 parts of the above-mentioned purified disproportionated rosin (acid value 180.0 mg KOH / g, softening point 84°C, color 4 Gardner) were charged. The temperature was raised to 185°C under a nitrogen seal, and under melting and stirring, 57 parts of glycerin were added at 200°C. The temperature was then raised to 280°C, and the esterification reaction was carried out at the same temperature for 14 hours to obtain 522 parts of purified disproportionated rosin ester with an acid value of 2.8 mg KOH / g and color 5 Gardner.

[0200] In a shaking autoclave, 200 parts of the purified disproportionated rosin ester and 2.5 parts of palladium carbon were charged. After removing oxygen from the system, the system was purified with hydrogen at a rate of 100 kg / cm³. 2The mixture was pressurized and heated to 260°C, and the hydrogenation reaction was carried out at the same temperature for 3.5 hours to obtain a hydrogenated rosin ester with an acid value of 13.3 mg KOH / g and a weight-average molecular weight of 730.

[0201] Manufacturing Example 2 200g of Chinese hydrogenated rosin (manufactured by Guangxi Wuzhou Rishen Forest Chemical Co., Ltd.), 2.5g of 5% palladium alumina powder (manufactured by N.E. Chemcat), and 200g of cyclohexane were charged into a 1L autoclave. After removing oxygen from the system, the system was pressurized to 7MPa with hydrogen and heated to 210°C. After reaching the temperature, the system was repressurized and maintained at 9MPa for 5 hours to carry out the hydrogenation reaction. After solvent filtration, 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 reactor equipped with a stirrer, condenser, and nitrogen inlet tube, melted to 200°C, then 22g of glycerin was added and the reaction was carried out at 280°C for 12 hours to obtain 173g of rosin ester with an acid value of 10.7mgKOH / g. 170 g of the obtained rosin ester was placed in a 1 L autoclave, along with 1.3 g of 5% palladium carbon (50% water content) and 170 g of cyclohexane. 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 for 5 hours to carry out the hydrogenation reaction. After solvent filtration, cyclohexane was removed under reduced pressure to obtain a hydrogenated rosin ester with an acid value of 10.6 mg KOH / g and a weight-average molecular weight of 780.

[0202] Manufacturing Example 3 In a reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and vacuum device, Chinese gum rosin with an acid value of 172.0 mgKOH / g, a softening point of 74°C, and a color of Gardner 6 was distilled under reduced pressure of 5 mmHg under a nitrogen seal. The main distillate, having an acid value of 175.0 mgKOH / g and a general constant of color of Gardner 4, was used as purified rosin.

[0203] In a reaction apparatus equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and vacuum device, 600 g of the purified rosin was charged, and the temperature was raised to 185°C under a nitrogen seal. At 200°C, 70 g of glycerin and 0.2 g of 5% palladium carbon (50% water content) as a disproportionation catalyst were added under molten stirring, and the temperature was raised to 280°C. The disproportionation and esterification reactions were carried out simultaneously at the same temperature for 11 hours to obtain a reaction product with an acid value of 2.9 mg KOH / g and a color of Gardner 4.

[0204] 200 g of the above reaction product and 1.2 g of 5% palladium carbon (50% water content) were placed in a 1 liter shaking autoclave. After removing oxygen from the system, the system was pressurized with hydrogen to 0.5 kg / cm² and heated to 280°C. The dehydrogenation reaction was carried out at the same temperature for 4 hours to obtain a disproportionate rosin ester with an acid value of 9.0 mg KOH / g and a weight-average molecular weight of 720.

[0205] Manufacturing Example 4 In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube, and steam inlet tube, 100 parts of Chinese gum rosin and 5 parts of maleic anhydride were charged. The mixture was then reacted at 220°C for 2 hours under a nitrogen gas stream. After that, 13.8 parts of pentaerythritol were charged, the temperature was raised to 280°C, and the mixture was reacted at the same temperature for 14 hours to complete the esterification. Subsequently, the reaction vessel was depressurized to remove water and other contaminants, 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.

[0206] Manufacturing Example 5 In a reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and vacuum device, Chinese gum rosin with an acid value of 172.0 mgKOH / g, a softening point of 74°C, and a color of Gardner 6 was distilled under reduced pressure of 5 mmHg under a nitrogen seal. The main distillate, having an acid value of 175.0 mgKOH / g and a general constant of color of Gardner 4, was used as purified rosin.

[0207] In a reaction vessel equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and vacuum device, 100 parts of the purified rosin and 13.3 parts of pentaerythritol were charged. The mixture was reacted at 250°C for 2 hours under a nitrogen gas stream, then the temperature was raised to 275°C and the reaction was continued at the same temperature for 15 hours to complete the esterification. After that, the reaction vessel was depressurized to remove water and other contaminants, and purified rosin ester was obtained.

[0208] In a shaking autoclave, 200 parts of the purified rosin ester and 1 part of palladium carbon were placed, and after removing oxygen from the system, the system was purified with hydrogen at a rate of 100 kg / cm³. 2 The mixture was pressurized and heated to 260°C, and a hydrogenation reaction was carried out at the same temperature for 3 hours to obtain a hydrogenated rosin ester with an acid value of 12.8 mg KOH / g and a weight-average molecular weight of 1,000.

[0209] Manufacturing Example 6 In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, and nitrogen and steam inlet tubes, 100 parts of rosin (acid value 172 mg KOH / g, softening point 77°C) were charged and melted at 160°C. Next, 18 parts of fumaric acid were charged, the temperature was raised to 225°C, and the reaction was carried out at that temperature for 2 hours. After that, 6 parts of glycerin were charged, the temperature was raised to 215°C, and the reaction was carried out at that temperature for 3.5 hours to obtain a fumaric acid-modified rosin ester with an acid value of 191.0 mg KOH / g and a weight-average molecular weight of 3,220.

[0210] Manufacturing example 7 A reaction vessel equipped with a stirring device, reflux condenser, thermometer, and nitrogen inlet tube / steam inlet tube, 68 parts of polymerized rosin (acid value 150 mg KOH / g, softening point 142°C) and 32 parts of rosin (acid value 172 mg KOH / g, softening point 77°C) were charged and melted at 215°C. Next, 11.5 parts of pentaerythritol were charged, the temperature was raised to 250°C, and the mixture was reacted at this temperature for 3 hours. Then, the temperature was further raised to 275°C and the mixture was reacted at this temperature for 9 hours. After that, the mixture was subjected to a reduced pressure treatment for 4 hours to obtain a polymerized rosin ester with an acid value of 6.6 mg KOH / g and a weight-average molecular weight of 2,400.

[0211] Manufacturing Example 8 In a reaction apparatus equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube, 200 parts of disproportionated rosin were charged and heated under a nitrogen stream until completely melted. Then, 113 parts of bisphenol A type polymer epoxy resin (epoxy equivalent 170) were added while stirring, and 0.1 parts of 2-methylimidazole were added at 150°C. The reaction was carried out at 160°C for 4 hours to obtain a rosin polyol with an acid value of 0.1 mg KOH / g and a weight-average molecular weight of 860.

[0212] Manufacturing Example 9 In a reaction apparatus equipped with a thermometer, stirrer, condenser, and nitrogen inlet, 300 parts of disproportionated rosin were charged and heated under a nitrogen stream until completely melted. Then, 113 parts of bisphenol A type polymer epoxy resin (epoxy equivalent 170) were added while stirring, and 0.1 parts of 2-methylimidazole were added at 150°C. The reaction was carried out at 160°C for 4 hours to obtain a rosin polyol with an acid value of 45.2 mgKOH / g and a weight-average molecular weight of 720.

[0213] Comparative Manufacturing Example 1 In a reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet tube, and vacuum device, Chinese gum rosin with an acid value of 172.0 mgKOH / g and a color of Gardner 6 was distilled under reduced pressure of 5 mmHg under a nitrogen seal, and the main distillate with an acid value of 175.0 mgKOH / g and a general constant of Gardner 4 was used as purified rosin.

[0214] In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube, and steam inlet tube, 100 parts of the purified rosin and 26 parts of fumaric acid were charged. The mixture was then reacted at 225°C for 3 hours under a nitrogen gas stream. After that, 1.5 parts of ethylene glycol and 7.5 parts of pentaerythritol were charged and the mixture was reacted at 250°C for 13 hours to obtain a fumaric acid-modified rosin ester with an acid value of 203.0 mgKOH / g and a weight-average molecular weight of 1,240.

[0215] Comparative Manufacturing Example 2 1000 parts of Chinese gum rosin (acid value 170, softening point 74°C, color 6 Gardner) and 500 parts of xylene were placed in a corvene and heated until dissolved. Approximately 350 parts of xylene were then removed by distillation, followed by the addition of 350 parts of cyclohexane. The mixture was then cooled to room temperature. When approximately 100 parts of crystals formed due to cooling, the supernatant was transferred to another corvene and recrystallized at room temperature. The supernatant was then removed, washed with 100 parts of cyclohexane, and the solvent was removed by distillation to obtain 700 parts of purified rosin.

[0216] 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 with stirring under a nitrogen stream. Then, unreacted material was removed under reduced pressure to obtain 720 parts of the addition reaction product. Furthermore, 500 parts of the obtained addition reaction product and 5.0 parts of 5% palladium carbon (water content 50%) were charged into a 1-liter rotary autoclave. 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 hydride of acrylic acid-modified rosin with an acid value of 240 mg KOH / g and a weight-average molecular weight of 360.

[0217] Comparative Manufacturing Example 3 In a reaction apparatus equipped with a thermometer, stirrer, condenser, and nitrogen inlet, 500 parts of disproportionated rosin were charged and heated under a nitrogen stream until completely melted. Then, 113 parts of bisphenol A type polymer epoxy resin (epoxy equivalent 170) were added while stirring, and 0.1 parts of 2-methylimidazole were added at 150°C. The reaction was carried out at 160°C for 4 hours to obtain a rosin polyol with an acid value of 86.0 mgKOH / g and a weight-average molecular weight of 550.

[0218] Comparative Manufacturing Example 4 1000 parts of Chinese gum rosin (acid value 170, softening point 74°C, color 6 Gardner) and 500 parts of xylene were placed in a corvene and heated until dissolved. Approximately 350 parts of xylene were then removed by distillation, followed by the addition of 350 parts of cyclohexane. The mixture was then cooled to room temperature. When approximately 100 parts of crystals formed due to cooling, the supernatant was transferred to another corvene and recrystallized at room temperature. The supernatant was then removed, washed with 100 parts of cyclohexane, and the solvent was removed by distillation to obtain 700 parts of purified rosin.

[0219] 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. Then, unreacted materials were removed under reduced pressure, and 5 parts of glycerin were added. The temperature was raised to 280°C and the reaction was carried out at the same temperature for 4 hours to complete the esterification. After that, the reaction vessel was depressurized to remove water and other substances, yielding 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. After removing oxygen from the system, the system was pressurized with hydrogen to 10 MPa and the temperature was raised to 220°C. The hydrogenation reaction was carried out at the same temperature for 3 hours to obtain a hydrogenated acrylic acid-modified rosin ester with an acid value of 226.5 mg KOH / g and a weight-average molecular weight of 430.

[0220] Comparative Manufacturing Example 5 100 parts of Chinese hydrogenated rosin (manufactured by Guangxi Wuzhou Rishen Forest Chemical Co., Ltd.) and 300 parts of methanol were charged into a 1 L autoclave. 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 carried out for 2 hours, blowing out the contents every 20 minutes. The resulting reaction solution was concentrated using a rotary evaporator, and 5 parts of calcium hydroxide were added, followed by simple distillation. Under conditions of a liquid temperature of 150-270°C and a pressure of 0.4 kPa, 6 parts of the initial distillate were removed, yielding 65 parts of rosin methyl ester as the main fraction, with an acid value of 1.0 mg KOH / g and a weight-average molecular weight of 240.

[0221] (Measurement of weight-average molecular weight (Mw)) The weight-average molecular weight (Mw) of the rosin-based resins in Production Examples 1-9 and Comparative Production Examples 1, 3-5 was calculated as a polystyrene equivalent value obtained from a calibration curve of standard polystyrene using gel permeation chromatography (GPC). The GPC method was measured under the following conditions. The results are shown in Table 1. Analytical instrument: HLC-8320 (manufactured by Tosoh Corporation) Column: TSKgelSuperHM-L x 3 Eluent: Tetrahydrofuran Injection sample concentration: 5 mg / mL Flow rate: 0.6mL / min Injection volume: 40μL Column temperature: 40℃ Detector: RI

[0222] The weight-average molecular weight (Mw) of the rosin-based resin in Comparative Production Example 2 was calculated as a polystyrene equivalent value obtained from a calibration curve of standard polystyrene using gel permeation chromatography (GPC). The GPC method was measured under the following conditions. The results are shown in Table 1. Analytical instrument: HLC-8320 (manufactured by Tosoh Corporation) Columns: TSK guardcolumn HH, TSK-GEL SUPER HM-L x 3 columns connected together Eluent: Tetrahydrofuran Injection sample concentration: 5 mg / mL Flow rate: 0.6mL / min Injection volume: 40μL Column temperature: 40℃ Detector: RI, UV (254nm)

[0223] (Measurement of acid value) The acid values ​​of the rosin-based resins in Production Examples 1-9 and Comparative Production Examples 1-5 were measured according to JIS K 0070. The results are shown in Table 1.

[0224] (Percentage of mass remaining after heating at 300°C for 2 hours) The mass residue percentage (%) of the rosin-based resins in Production Examples 1-9 and Comparative Production Examples 1-5 after heating at 300°C for 2 hours was calculated using a differential thermal and gravimetric analyzer (Hitachi High-Tech Science Co., Ltd., instrument name "STA7200") under nitrogen atmosphere conditions, with a sample mass of 10 mg and a nitrogen flow rate of 250 ml / min. The sample mass was increased from 30°C to 300°C at a rate of 10°C / min, and then heated at 300°C for 2 hours. The percentage was calculated from (sample mass after heating) / (sample mass before heating) × 100 (%). The results are shown in Table 1.

[0225] While methods using thermogravimetric differential thermal analysis (TG / DTA) or thermogravimetric analysis (TGA) to measure weight loss upon heating include measuring the temperatures at which weight loss reaches 1%, 3%, and 5% under conditions such as heating rates of 5°C / min and 10°C / min (1% weight loss temperature, 3% weight loss temperature, and 5% weight loss temperature), the inventors' investigations revealed that these weight loss temperatures are insufficient to adequately evaluate the tendency of smoke generation during the melting of thermoplastic resins in rosin-based resins.

[0226] For example, the 5% weight loss temperature of the rosin resin in Production Example 5 is 267°C, while the 5% weight loss temperature of the rosin resin in Comparative Production Example 2 is 256°C. There is no significant difference between the two. However, as shown in Table 1, the mass retention rate (%) after heating at 300°C for 2 hours is 86% for the rosin resin in Production Example 5, compared to 10% for the rosin resin in Comparative Production Example 2, showing a significant difference. Furthermore, as shown in Table 2 below, smoke generation is suppressed in pellets using the rosin resin in Production Example 5, while smoke generation is significantly higher in pellets using the rosin resin in Comparative Production Example 2.

[0227] The 5% weight loss temperature of the rosin-based resins in Manufacturing Example 5 and Comparative Manufacturing Example 2 was measured using a differential thermal and gravimetric simultaneous measurement device (Hitachi High-Tech Science Co., Ltd., device name "STA7200") under a nitrogen atmosphere, with a sample volume of 10 mg, measurement temperature of 30-500 °C, heating rate of 10 °C / min, and nitrogen flow rate of 250 ml / min, at which point the sample weight decreased by 5%.

[0228] (Measurement of mixed methylcyclohexaneaniline cloud point (°C) (MMAP)) The cloud point (°C) (MMAP) of mixed methylcyclohexaneaniline rosin resins for Production Examples 1-9 and Comparative Production Examples 1-5 was determined by heating a homogeneous solution containing 1 g of each component, 1 mL of methylcyclohexane, and 2 mL of aniline, and then cooling it until turbidity occurred. The temperature at which turbidity appeared in the solution was measured. The results are shown in Table 1.

[0229] [Table 1]

[0230] The annotations in Table 1 are as follows. ※ Mass residue ratio after heating at 300°C for 2 hours

[0231] [Preparation of Resin Composition and Molded Body] Example 1 Into a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Laboplast Mill Model 10C100"), 100 parts of a modified polyphenylene ether resin (manufactured by Global Polyacetal Co., Ltd., trade name "Upi Ace AH40") and 3 parts of the rosin-based resin of Production Example 1 as a modifier were charged, and kneaded at a roller rotation speed of 40 rpm and a temperature of 250°C for 10 minutes. Then, the obtained kneaded product (resin composition) was taken out from the kneading device, hot pressed at 250°C, molded into a sheet with a thickness of 1.0 mm, and cut into 5 mm × 5 mm with a cutting machine to obtain pellets.

[0232] Example 2 In Example 1, preparation was carried out in the same manner as in Example 1 except that 5 parts of the rosin-based resin of Production Example 1 was used as a modifier, and pellets were obtained.

[0233] Examples 3 to 10 In Example 1, preparation was carried out in the same manner as in Example 1 except that the rosin-based resin of Production Example 1 was changed to the rosin-based resins of Production Examples 2 to 9 as a modifier, and pellets were obtained.

[0234] Comparative Example 1 Into a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Laboplast Mill Model 10C100"), 100 parts of a modified polyphenylene ether resin (manufactured by Global Polyacetal Co., Ltd., trade name "Upi Ace AH40") was charged, and kneaded at a roller rotation speed of 40 rpm and a temperature of 250°C for 10 minutes. Then, the obtained kneaded product (resin composition) was taken out from the kneading device, hot pressed at 250°C, molded into a sheet with a thickness of 1.0 mm, and cut into 5 mm × 5 mm with a cutting machine to obtain pellets.

[0235] Comparative Examples 2 to 6 In Example 1, the preparation was carried out in the same manner as in Example 1, except that the rosin resin used as the modifier was replaced with the rosin resins used in Comparative Production Examples 1 to 5, to obtain pellets.

[0236] (Smoke emission evaluation) When pellets from Examples 1-10 and Comparative Examples 1-6 were injection molded at 290°C using a Hand Truder M-1 (manufactured by Toyo Seiki Seisakusho Co., Ltd., a tabletop manual injection molding machine / pelletizer), smoke generation during molding was visually evaluated and assessed according to the following criteria. The results are shown in Table 2. ○: There is almost no smoke. △: A small amount of smoke is produced. ×: Produces a lot of smoke.

[0237] (MFR evaluation) In accordance with JIS K 7210, the MFR of each pellet from Examples 1-10 and Comparative Examples 1-6 was measured under conditions of a temperature of 300°C and a load of 21.2 N (2.16 kg).

[0238] Then, the rate of increase in MFR of the pellets from Examples 1-10 and Comparative Examples 2-6 compared to Comparative Example 1 (blank) was evaluated according to the following criteria. The results are shown in Table 2. The higher the rate of increase in MFR, the better the moldability, and if the evaluation is ○, it can be used without practical problems. ○: MFR increase of 30% or more compared to the blank. △: MFR increase rate is between 10% and 30% compared to the blank. ×: MFR increase rate is less than 10% compared to the blank.

[0239] [Table 2]

[0240] The amounts in Table 2 are given in parts by mass. The abbreviations and notes in Table 2 are as follows: *Due to excessive smoke generation, pellet preparation was not possible, so MFR was not measured. mPPE: Modified polyphenylene ether resin, trade name "Yupiace AH40", manufactured by Global Polyacetal Co., Ltd.

[0241] [Preparation of resin compositions and molded articles] Example 10 100 parts of polyamide (manufactured by Asahi Kasei Corporation, product name "Leona 1700S") and 5 parts of the rosin-based resin from Production Example 1 as a modifier were added to a roller mixer type kneading device (manufactured by Toyo Seiki Mfg. Co., Ltd., device name "Laboplastmill Model 10C100"), and the mixture was kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 290°C. After that, the resulting mixture (resin composition) was removed from the kneading device, hot-pressed at 290°C to form a sheet with a thickness of 1.0 mm, and then cut into 5 mm x 5 mm pieces using a cutting machine to obtain pellets.

[0242] Example 11 In Example 10, the preparation was carried out in the same manner as in Example 10, except that 8 parts of the rosin-based resin from Production Example 1 were used as a modifier, and pellets were obtained.

[0243] Examples 12-17 In Example 10, the preparation was carried out in the same manner as in Example 10, except that the rosin-based resin of Production Example 1 was replaced with the rosin-based resins of Production Examples 2-4, 6, and 8-9 as the modifier, and pellets were obtained.

[0244] Comparative Example 7 100 parts of polyamide (manufactured by Asahi Kasei Corporation, product name "Leona 1700S") were put into a roller mixer type kneading device (manufactured by Toyo Seiki Mfg. Co., Ltd., device name "Laboplastmill Model 10C100") and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 290°C. After that, the resulting kneaded material (resin composition) was removed from the kneading device, hot-pressed at 290°C to form a sheet with a thickness of 1.0 mm, and then cut into 5 mm x 5 mm pieces using a cutting machine to obtain pellets.

[0245] Comparative Example 8 In Example 10, pellets were obtained in the same manner as in Example 10, except that the rosin-based resin of Production Example 1 was changed to the rosin-based resin of Comparative Production Example 5 as a modifier.

[0246] (Evaluation of smoke generation) When the pellets of Examples 10 to 17 and Comparative Examples 7 to 8 were injection molded at 290 °C using a hand extruder M-1 (manufactured by Toyo Seiki Seisakusho Co., Ltd., bench top manual injection molding machine / pelletizer), the smoke generation during molding was visually evaluated, and the smoke generation was evaluated according to the following criteria. The results are shown in Table 3. 〇: Almost no smoke generation. △: A little smoke generation. ×: A lot of smoke generation.

[0247] (Evaluation of MFR) In accordance with JIS K 7210, the MFR of the pellets of Examples 10 to 17 and Comparative Examples 7 to 8 was measured under the conditions of a temperature of 290 °C and a load of 21.2 N (2.16 kg).

[0248] Then, the increase rate of the MFR of the pellets of Examples 10 to 17 and Comparative Example 8 with respect 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 the MFR, the better the molding processability. 〇: The increase rate of MFR is 300% or more compared to the blank. △: The increase rate of MFR is 150% or more and less than 300% compared to the blank. ×: The increase rate of MFR is less than 150% compared to the blank.

[0249]

Table 3

[0250] The compounding amounts in Table 3 are values in parts by mass. The abbreviations and notes in Table 3 are as follows. ※ Since a large amount of smoke was generated and pellets could not be prepared, the MFR was not measured. PA: Polyamide, trade name "Leonar 1700S", manufactured by Asahi Kasei Corporation

[0251] [Preparation of resin compositions and molded articles] Example 18 70 parts of polypropylene (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "Laboplastmill Model 10C100"), 30 parts of cellulose fiber (manufactured by Rettenmeyer, product name "Arbocell BC1000"), and 5 parts of the rosin-based resin from Production Example 3 as a modifier were added to a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "PMB60A"), 30 parts of cellulose fiber (manufactured by Rettenmeyer, product name "Arbocell BC1000"), and 5 parts of the rosin-based resin from Production Example 3 as a modifier. The mixture was kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 190°C. After that, the resulting mixture (resin composition) was removed from the kneading device, hot-pressed at 200°C to form a sheet with a thickness of 1.0 mm, and then cut into 5 mm x 5 mm pieces using a cutting machine to obtain pellets.

[0252] Examples 19-21 In Example 18, the preparation was carried out in the same manner as in Example 18, except that the rosin-based resin of Production Example 3 was replaced with the rosin-based resin of Production Examples 6, 8-9 as the modifier, and pellets were obtained.

[0253] Comparative Example 9 70 parts of polypropylene (manufactured by Sun Allomer Co., Ltd., product name "PMB60A") and 30 parts of cellulose fiber (manufactured by Rettenmeyer, product name "Arbocell BC1000") were added to a roller mixer type kneading device (manufactured by Toyo Seiki Seisakusho Co., Ltd., device name "Labo Plast Mill Model 10C100"), and kneaded for 10 minutes at a roller rotation speed of 40 rpm and a temperature of 190°C. After that, the resulting kneaded material (resin composition) was removed from the kneading device, hot-pressed at 200°C to form a sheet with a thickness of 1.0 mm, and then cut into 5 mm x 5 mm pieces using a cutting machine to obtain pellets.

[0254] Comparative Examples 10-11 In Example 18, the preparation was carried out in the same manner as in Example 18, except that the rosin-based resin of Production Example 3 was replaced with the rosin-based resin of Comparative Production Examples 1 and 5 as the modifier, and pellets were obtained.

[0255] (Smoke emission evaluation) When pellets from Examples 18-21 and Comparative Examples 9-11 were injection molded at 200°C using a Hand Truder M-1 (manufactured by Toyo Seiki Mfg. Co., Ltd., a tabletop manual injection molding machine / pelletizer), smoke generation during molding was visually evaluated and assessed according to the following criteria. The results are shown in Table 4. ○: There is almost no smoke. △: A small amount of smoke is produced. ×: Produces a lot of smoke.

[0256] (MFR evaluation) In accordance with JIS K 7210, the MFR of each pellet from Examples 18-21 and Comparative Examples 9-11 was measured under conditions of a temperature of 190°C and a load of 49.0 N (5 kg).

[0257] Then, the rate of increase in MFR of the pellets from Examples 18-21 and Comparative Examples 10-11 compared to Comparative Example 9 (blank) was evaluated according to the following criteria. The results are shown in Table 4. A higher rate of increase in MFR indicates better moldability. ○: MFR increase rate of 100% or more compared to the blank. △: MFR increase rate is between 50% and 100% compared to the blank. ×: MFR increase rate is less than 50% compared to the blank.

[0258] (Evaluation of bending stress) The resin compositions of Examples 18-21 and Comparative Examples 9-11 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 specimens (length 80 mm x width 10 mm x thickness 4 mm). The bending stress (MPa) of the prepared rectangular test specimens was measured using a Tensilon universal testing machine (product name "RTG-1210", manufactured by A&D Co., Ltd.) in accordance with JIS K7171, with a support distance of 64 mm, a test speed of 2 mm / min, a temperature of 23°C, and a 50% RH environment. The results are shown in Table 4.

[0259] [Table 4]

[0260] The amounts in Table 4 are given in parts by mass. The abbreviations and notes in Table 4 are as follows: *Due to excessive smoke generation, pellet preparation was not possible, so MFR was not measured. PP: Polypropylene, product name "PMB60A", manufactured by Sun Allomer Co., Ltd. Cellulose: Cellulose fiber, trade name "Arbocell BC1000", manufactured by Rettenmeyer GmbH.

Claims

1. The mass residue rate after heating at 300°C for 2 hours is 40% by mass or more. The mixed methylcyclohexaneaniline cloud point (MMAP) is -10 to 20°C. The acid value is 200 mg KOH / g or less. Contains rosin-based resins, It is a modifier for thermoplastic resins, The thermoplastic resin comprises at least one selected from the group consisting of polyamide, polyphenylene ether, and polyolefin resin. A modifier for thermoplastic resins.

2. The modifier and thermoplastic resin described in claim 1 are included, The thermoplastic resin comprises at least one selected from the group consisting of polyamide, polyphenylene ether, and polyolefin resin. Resin composition.

3. Furthermore, the resin composition according to claim 2, further comprising a filler.

4. The resin composition according to claim 3, wherein the filler comprises at least one selected from the group consisting of glass fibers, carbon powder, calcium carbonate, cellulose powder, and cellulose fibers.

5. The use of the rosin-based resin described in claim 1 as a modifier for thermoplastic resins is as follows: The thermoplastic resin comprises at least one selected from the group consisting of polyamide, polyphenylene ether, and polyolefin resin. Use of rosin-based resin.

6. The use according to claim 5, wherein the thermoplastic resin further comprises a filler.

7. The use of the rosin-based resin according to claim 1 for producing a resin composition containing a thermoplastic resin, The thermoplastic resin comprises at least one selected from the group consisting of polyamide, polyphenylene ether, and polyolefin resin. Use of rosin-based resin.

8. The use according to claim 7, wherein the resin composition further comprises a filler.

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