JPWO2014185324A1 - RESIN COMPOSITION, MOLDED BODY USING THE RESIN COMPOSITION, AND METHOD FOR PRODUCING MOLDED BODY - Google Patents

Abstract

[PROBLEMS] To provide good adhesion to olefinic resins such as cross-linked polyethylene-coated electric wires and polypropylene, and also has good adhesion to general-purpose resins such as PBT, and also has good flexibility. It is providing the resin composition which has. When the crystalline copolyester is 100 parts by weight, 5 to 15 parts by weight is an amorphous resin, 15 to 25 parts by weight is an acid-modified polyolefin, and 15 to 25 parts by weight is an acid. A resin composition which is an unmodified polyolefin. [Selection figure] None

Description

  The present invention relates to a resin composition, a method for producing a molded body using the resin composition, and a molded body.

Olefin-based resins such as polypropylene (PP) and polyethylene (PE) are widely used in various fields including automobiles and home appliances because they are low in price and light, and have excellent strength, chemical resistance, and hydrolysis resistance. . Particularly in recent years, weight reduction has been strongly demanded for improving the fuel efficiency of automobiles, and glass fiber reinforced polypropylene has been widely studied as a substitute for metal. Conventionally, vinyl chloride (vinyl chloride) has been mainly used as a covering material for electric wires used in electric and electronic parts, but in recent years, cross-linked polyethylene-coated electric wires have been widely used from the viewpoint of environmental problems and heat resistance. It has come to be.
However, since these olefin-based resins such as polypropylene and polyethylene have no polarity, there is no resin having good adhesion to molded articles, electrical / electronic parts, or films using these, for example, polyethylene terephthalate ( In order to form a composite with a resin such as PET or polybutylene terephthalate (PBT) or a metal, it was necessary to make a hole and fix it with a screw.

  On the other hand, electrical and electronic parts used in automobiles and electrical appliances are connected to the outside by electric wires in order to receive external power supply and send electrical signals to the outside. Requires electrical insulation from the outside and is sealed with an insulating resin or the like. Up to now, two-component curable epoxy resins and silicone resins have been generally used in consideration of the durability after sealing, but they have an adhesive force for cross-linked polyethylene-coated electric wires and polypropylene housings. In some cases, water or the like enters from the interface between the electric wire or the casing and the sealing material, resulting in poor insulation, and there is a possibility that the electric and electronic parts are destroyed due to shrinkage stress at the time of curing.

Therefore, in recent years, a hot-melt type resin has been proposed as a sealing resin that replaces the two-component curable epoxy resin. Hot melt resin has a merit that the work efficiency is drastically improved compared to two-part curable epoxy resin because viscosity is lowered and electrical and electronic parts can be easily sealed simply by heating and melting. Polyamide that exhibits high adhesion to various materials is excellent as a low-pressure injection molding resin material due to its low melt viscosity and high resin strength (see, for example, Patent Document 1), but has no adhesion to crosslinked polyethylene. Similar to the two-component curable epoxy, water may enter from the interface between the wire and the sealing material, resulting in poor insulation, and is basically the most important characteristic because it is highly hygroscopic. In many cases, it was difficult to ensure insulation. On the other hand, polyesters with high electrical insulation and water resistance are considered to be very useful materials for this application, but polyesters developed for hot melt adhesives (for example, Patent Document 2) still have adhesive strength to crosslinked polyethylene. Not only may the water resistance and insulation properties be poor, but the melt viscosity is generally high, and injection molding at high pressures of several tens to several hundreds of MPa is required to seal parts with complex shapes. There is a risk of destroying the electrical / electronic component to be sealed. Polyester developed for molding electrical and electronic parts (for example, Patent Document 3) has a low melt viscosity and enables low-pressure molding, and can be sealed without destroying electrical and electronic parts. Polypropylene, crosslinked polyethylene, etc. The adhesive strength to the wire has not been improved, and it has not been possible to prevent the ingress of water from the interface of the electric wire, which has the major drawback of hindering the original electrical insulation.
As a resin composition having improved adhesion to cross-linked polyethylene or polypropylene, a low-pressure molding resin composition mainly composed of an olefin resin has been proposed (for example, Patent Document 4), but the elongation as a resin composition is also proposed. Because of its small size and poor flexibility, it has been difficult to apply it to electric and electronic parts such as electric wires in which bendability is important.

  As described above, in the prior art, a material that sufficiently satisfies all required performances has not been proposed as a resin for sealing electrical and electronic parts.

JP 2001-24550 A JP 60-18562 A Japanese Patent No. 3553559 JP 2012-180385 A

  The problem of the present invention is that it has good adhesion to olefinic resins such as cross-linked polyethylene-coated electric wires and polypropylene, and also has good adhesion to general-purpose resins such as PBT, and also good flexibility. It is providing the resin composition which also has property.

In order to achieve the above object, the present inventors have intensively studied and have proposed the following invention. That is, the present invention relates to the following resin composition, a molded body using the resin composition, and a method for producing the molded body.
(1) A crystalline copolymer polyester, an amorphous resin, an acid-modified polyolefin, and a non-acid-modified polyolefin are contained. When the crystalline copolymer polyester is 100 parts by mass, 3 to 18 parts by mass A resin composition that is an amorphous resin, 10 to 30 parts by mass of an acid-modified polyolefin, and 10 to 30 parts by mass of a polyolefin that is not acid-modified. (2) The resin composition according to (1), wherein the melt viscosity at 200 ° C. is 100 Pa · s or less.
(3) The resin composition according to any one of (1) and (2), wherein the crystalline copolymer polyester contains an ether bond. The resin composition according to any one of (1) to (3), having a glass transition temperature of 0 ° C. or lower.
(5) The resin composition according to any one of (1) to (4), wherein the amorphous resin is an amorphous copolyester resin. (6) The acid-modified polyolefin is an acid-modified polypropylene. The resin composition according to any one of claims (1) to (5), wherein:
(7) The resin composition according to any one of (1) to (6), wherein the non-acid-modified polyolefin has an ethylene chain or a propylene chain as a main component.
(8) The crystalline viscosity polyester, the amorphous resin, the acid-modified polyolefin, and the non-acid-modified polyolefin all have a melt viscosity at 200 ° C. of 200 Pa · s or less (2) to (7) The resin composition in any one.
(9) A molded body using the resin composition according to any one of (1) to (8).
(10) Manufacture of the molded object which uses the resin composition in any one of (1)-(8), and seals an electric and electronic component by insert molding at the pressure of 20 Mpa or less and the temperature of 280 degrees C or less. Method.
(11) The method for producing a molded article according to (10), wherein the electric and electronic parts are subjected to an easy adhesion surface treatment.
(12) The method for producing a molded article according to (11), wherein the easy adhesion surface treatment is a plasma treatment or a flame treatment under atmospheric pressure.
(13) The method for producing a molded article according to (12), wherein the flame treatment uses a flame in which a silicon compound is burned.
(14) A molded body produced by the method according to any one of (10) to (13).

The resin composition of the present invention has good adhesive strength to polyolefin resins that could not ensure good adhesive strength with conventional polyester resins and polyamide resins such as crosslinked polyethylene-coated electric wires and polypropylene molded articles, and A resin composition having good flexibility is provided.
Furthermore, when low-pressure insert molding of electrical and electronic parts, etc., it can be melt-molded at a low temperature and low pressure that does not damage the electrical and electronic parts, and can exhibit good electrical insulation. Thus, a high level of waterproofness can be imparted to the electrical / electronic component sealed body. For this reason, by using the resin composition of the present invention, it is possible to produce a sealed electrical and electronic part having a high level of waterproofness.

It is a schematic diagram which shows the external appearance and sectional structure of the sealing body sample for moldability evaluation.

  The resin composition of the present invention can be used for various applications, but can be used particularly for low-pressure insert molding of electric and electronic parts. In general, low-pressure insert molding of electric and electronic parts is performed by placing a substrate on which electric and electronic parts are mounted in a mold and heating and melting the resin composition for sealing to give fluidity at a low pressure of 0.1 to 20 MPa. This is a molding method that is carried out by extruding into a mold and used for manufacturing an electric / electronic component sealing body. In other words, since it is performed at a very low pressure compared to the injection molding at a high pressure of 40 MPa or more that is conventionally used for plastic molding, without destroying the electric and electronic parts limited in heat resistance and pressure resistance. It can be sealed. By selecting the resin composition of the present invention as the sealing resin composition, a crosslinked polyethylene-coated electric wire, a polypropylene resin, a polyester base material such as PET or PBT, a glass epoxy substrate (Garaepo: glass fiber cloth ( Cross) and epoxy resin impregnated), metal and other materials that make up electrical and electronic parts, giving good adhesion to the environment and high environmental resistance. It is possible to obtain a sealed body having adhesion durability that can withstand the above. Below, the detail of the form for inventing is demonstrated one by one.

  The resin composition of the present invention comprises a crystalline copolyester, an amorphous resin, an acid-modified polyolefin, and a non-acid-modified polyolefin. When the crystalline copolyester is 100 parts by mass, 3 It is essential that -18 parts by mass is an amorphous resin, 10-30 parts by mass is an acid-modified polyolefin, and 10-30 parts by mass is a resin composition that is not acid-modified polyolefin. By blending these four types of components, it is possible to express good adhesion to crosslinked polyethylene, polypropylene, PBT, glass epoxy, and the like, as well as the crystallization speed and the sealing resin composition during the manufacture of the sealing body. Since the degree of crystallinity can be adjusted, stress concentration during crystallization can be relaxed, and the adhesive strength to the substrate can be further increased.

  The resin composition used in the present invention preferably has a melt viscosity at 200 ° C. of 100 Pa · s or less from the viewpoint of moldability. The pressure is preferably 80 Pa · s or less, more preferably 70 Pa · s or less. If the melt viscosity exceeds 100 Pa · s, the melt viscosity becomes too high at a temperature that does not damage electrical and electronic parts, and in order to ensure good moldability, the temperature and pressure must be increased during molding, Damage to electrical and electronic parts. In order to reduce the melt viscosity to 100 Pa · s or less, it is important to lower the melt viscosity of the crystalline copolymer polyester occupying the largest volume as the composition, and the melt viscosity of the crystalline copolymer polyester is 100 Pa · s or less. It is desirable to be. Regarding the amorphous resin, the acid-modified polyolefin, and the non-acid-modified polyolefin, the melt viscosity at 200 ° C. is preferably 200 Pa · s or less, and more preferably 180 Pa · s or less.

The crystalline copolyester used in the present invention is preferably used by blending two or more types of crystalline copolyester. By using two or more types of crystalline copolyesters, it is possible to adjust the crystallization speed during the production of the encapsulant and the crystallinity of the encapsulating resin composition, thereby reducing stress concentration during crystallization. And the adhesion strength to the substrate can be further increased. For example, by blending polyester with fast crystallinity with polyester with slow crystallinity, the polyester with fast crystallinity plays a role in improving mold releasability from the mold, and stress relaxation during crystallization with polyester with slow crystallinity. It is possible to play a role of improving adhesiveness.

The crystalline copolyester used in the present invention preferably has an ether bond in the molecule, and preferably has a glass transition temperature of 0 ° C. or lower. By having an ether bond in the molecule, the melt viscosity of the resin can be lowered and the glass transition temperature can be lowered. Since the glass transition temperature greatly contributes to the thermal cycle characteristics, it is more preferably −20 ° C. or lower. The crystalline copolyester in the present invention is a differential scanning calorimeter “DSC220 type” manufactured by Seiko Denshi Kogyo Co., Ltd., and 5 mg of a measurement sample is put in an aluminum pan and sealed with a lid once. Hold the sample at 5 ° C for 5 minutes to completely melt the sample, then quench with liquid nitrogen, and then show a melting point when measured from -150 ° C to 250 ° C at a heating rate of 20 ° C / min. Point to.

  The crystalline copolyester used in the present invention can be obtained, for example, by dehydration condensation or dealcoholization condensation of an acid component such as a dibasic acid or its anhydride or an alkyl ester and a glycol component.

Examples of the dibasic acid compound include terephthalic acid, isophthalic acid, orthophthalic acid, 1,2-naphthalenedicarboxylic acid, aromatic dibasic acid such as 1,6-naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid, Sebacic acid, dodecanoic acid, dimer acid, hydrogenated dimer acid, dodecenyl succinic anhydride, fumaric acid, dodecanedioic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2- Examples thereof include aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and alicyclic dicarboxylic acids.
Of these dibasic acid compounds, terephthalic acid or 1,6-naphthalenedicarboxylic acid is preferably contained in an amount of 50 mol% or more of the total dibasic acid compound from the viewpoints of crystallinity, heat resistance, and hydrolysis resistance. . Furthermore, it is more preferable to contain 60 mol% or more.

The glycol component includes ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol. 1,4-butylene glycol, 2-methyl-1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl- 1,3-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2 ′, 2′-dimethyl- 3′-hydroxypropanoate, 2- (n-butyl) -2-ethyl-1, -Propanediol, 3-ethyl-1,5-pentanediol, 3-propyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol and the like Aliphatic diols such as 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) cyclohexane, 1,4-bis (hydroxypropyl) cyclohexane 1,4-bis (hydroxymethoxy) cyclohexane, 1,4-bis (hydroxyethoxy) cyclohexane, 2,2-bis (4-hydroxymethoxycyclohexyl) propane, 2,2-bis (4-hydroxyethoxycyclohexyl) propane Bis (4-hydroxycyclohexyl) methane 2,2-bis (4-hydroxycyclohexyl) propane, 3 (4), 8 (9) - tricyclo [5.2.1.0 ^{2, 6]} alicyclic glycols such as decane dimethanol, or Bisphenol A Aromatic glycols such as ethylene oxide adducts and propylene oxide adducts, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol and the like. Among these, ethylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol and the like are preferably used in an amount of 50 mol% or more of the total glycol component of the crystalline copolymer polyester because it is easy to express crystallinity. .

  Furthermore, in the crystalline copolyester used in the present invention, a part of the dibasic acid component is replaced with a trifunctional or higher carboxylic acid, or a part of the glycol component is replaced with a trifunctional or higher functional polyol, It can also be copolymerized. These tri- or higher functional compounds include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) and many others. And polyfunctional glycols such as trivalent carboxylic acids and their anhydrides, trimethylolpropane, pentaerythritol, glycerin and polyglycerin. The copolymerization amount of the tri- or higher functional compound is preferably 0 to 5 mol% in all components from the viewpoints of crystallinity and reactivity.

  Further, the crystalline copolyester used in the present invention can be copolymerized or post-added with glycolic acid, lactones, lactides, or (poly) carbonates, or post-added or copolymerized with acid anhydrides.

  As described above, the crystalline copolyester used in the present invention preferably has an ether bond in the molecule, and it is desirable to copolymerize a compound having an ether bond. Examples of the compound having an ether bond include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol. Polytetramethylene glycol is desirable from the viewpoint of enhancing crystallinity.

  The resin composition used in the present invention must contain 3 to 18 parts by mass of an amorphous resin when the content of the crystalline copolyester is 100 parts by mass. The amorphous resin serves to disperse the acid-modified polyolefin or non-acid-modified polyolefin in the crystalline copolyester, and the blending ratio of the amorphous resin is preferably 5 parts by mass or more and 15 parts by mass or less, and more preferably. Is 7 parts by mass or more and 13 parts by mass or less. If the blending amount of the amorphous resin is too small, the dispersion of the olefin resin becomes poor, and if the blending amount is too large, the resin composition may become brittle.

Examples of the amorphous resin include amorphous copolymer polyester, epoxy resin, polyamide, olefin resin, polycarbonate, acrylic resin, ethylene vinyl acetate resin, and phenol resin.

  Preferred amorphous resins include amorphous copolyesters and epoxy resins. Amorphous polyester is obtained by dehydration condensation or dealcoholization condensation of an acid component such as a dibasic acid or its anhydride or an alkyl ester and a glycol component in the same manner as the above-mentioned crystalline copolyester. The same polyester as the copolyester can be used, but a large amount of raw materials having side chains such as neopentyl glycol and 1,2-propylene glycol are used so as not to have crystallinity, and isophthalic acid and orthophthalic acid are used. It is necessary to select raw materials that break linearity.

The resin composition used in the present invention must contain 10 to 30 parts by mass of acid-modified polyolefin when the content of the crystalline copolyester is 100 parts by mass. The acid-modified polyolefin acts as a compatibilizer between the amorphous resin and the non-acid-modified polyolefin.
The addition amount of the acid-modified polyolefin is preferably 13 to 27 parts by mass, more preferably 15 to 25 parts by mass.
If the amount of the acid-modified polyolefin is too small, the adhesiveness to a substrate such as glass epoxy is lowered. On the other hand, if the amount is too large, the adhesiveness to PBT may be lowered.

The acid-modified polyolefin used in the present invention is obtained by graft-polymerizing at least one selected from the group consisting of unsaturated carboxylic acids having 3 to 10 carbon atoms, acid anhydrides and esters thereof onto an olefin resin. Is preferred. The weight of the graft chain based on the whole acid-modified polyolefin is preferably 0.5 to 10% by weight. More preferably, it is 1 to 6% by weight. If the weight fraction of the graft chain is too small, the adhesion to a substrate such as a glass-epoxy base material is lowered, and if it is too much, the hygroscopicity tends to increase.

  Examples of the acid-modified polyolefin used as the base of the acid-modified polyolefin used in the present invention include polyethylene, polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-propylene-butene copolymer. Polypropylene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer are desirable in terms of heat resistance and compatibility with other resins. In addition, as acid-modified polyolefins, those obtained by copolymerizing unsaturated acids such as (meth) acrylic acid esters and (meth) acrylic acids and alkyl esters of unsaturated acids, vinyl acetate, ethylene, propylene and α-olefins are also available. Can be used.

  Examples of unsaturated carboxylic acids having 3 to 10 carbon atoms, acid anhydrides and esters thereof used for acid modification include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid. Examples include acid anhydrides of unsaturated carboxylic acids such as acid, maleic anhydride, itaconic anhydride and citraconic anhydride, and alkyl esters of unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate and dimethyl maleate. Among these, maleic acid, itaconic acid and acid anhydrides thereof are preferable in terms of reactivity.

  The graft polymerization for producing the acid-modified polyolefin in the present invention can be carried out by a known method, and the method is not particularly limited. For example, an organic peroxide is added to a molten mixture of the polyolefin and the unsaturated carboxylic acid component or to a mixture solution obtained by dissolving the polyolefin and the unsaturated carboxylic acid component in a solvent such as toluene or xylene. It can be carried out. When performing graft polymerization, it is preferable to avoid mixing of air and oxygen, and it is preferable to carry out in inert gas atmosphere, such as nitrogen gas. Examples of the organic peroxide include acetylcyclohexylsulfonyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, and the like.

  It is essential that the resin composition used in the present invention contains 10 to 30 parts by mass of a non-acid-modified polyolefin when the content of the crystalline copolymer polyester is 100 parts by mass. Polyolefin which is not acid-modified is present in an island state in the resin composition, and plays a role of relieving stress when the crystalline copolymerized polyester in the sea state undergoes crystallization shrinkage. The addition amount of the non-acid-modified polyolefin is preferably 13 to 27 parts by mass, more preferably 15 to 25 parts by mass. If the amount of non-acid-modified polyolefin is too small, the stress cannot be relaxed and the adhesiveness to various substrates may be lowered, and if too much, the adhesiveness to PBT or the like may be lowered.

The non-acid-modified polyolefin used in the present invention may be not only general-purpose olefins such as polyethylene and polypropylene, but also polycycloolefins. Moreover, what copolymerized ethylene, propylene, alpha olefin, etc. may be used.
As the non-acid-modified polyolefin, a polymer having a propylene chain as a main component or a polymer having an ethylene chain as a main component is preferable.
A polymer having a propylene chain as a main component (propylene-based resin) refers to a polymer containing 50% by mass or more of a propylene component, and includes homopolypropylene, a copolymer of propylene and ethylene, a copolymer of propylene and an α-olefin, and the like. These can also be used in a blend.

  The polymer (ethylene-based resin) having an ethylene chain as a main component refers to a polymer containing 50% by mass or more of an ethylene component, such as homopolyethylene, a copolymer of ethylene and propylene, a copolymer of ethylene and α-olefin, and the like. These can be used alone, or can be blended for use.

In the present invention, the α-olefin specifically refers to butene, pentene, hexene, octene, 4-methylpentene and the like, and has a carbon-carbon double bond of 4 or more carbon atoms and only one at the α-position. Refers only to unsaturated hydrocarbons.

  The resin composition of the present invention preferably has a phase separation structure after melting, and desirably has a sea-island structure or a bicontinuous structure. In the present invention, the sea-island structure refers to a phase separation structure in which one of the phase separation structure domains forms a continuous phase and the other domain forms a discontinuous phase. In the present invention, the co-continuous structure refers to a phase-separated structure in which two of the phase-separated structure domains form a continuous phase and the other domains form a discontinuous phase. . Needless to say, it is necessary to adjust the ratio of each compound in order to develop the phase separation structure, and it is also greatly affected by the temperature and time during kneading, screw configuration, screw rotation speed, etc. Needless to say. If the temperature or rotational speed is increased too much, molecular chains may be cut or cross-linked.

  In the sea-island structure of the resin composition of the present invention, the sea part (continuous phase) is preferably a crystalline copolymer polyester, and the island part (dispersed phase) is a polymer mainly composed of ethylene chains or propylene chains. desirable.

  The composition of the present invention has a phase-separated structure, in particular, a sea-island structure or a co-continuous structure, so that the characteristics of each component are excellent without averaging, particularly heat resistance and adhesion to a substrate. It becomes possible to express.

  The phase separation structure of the resin composition of the present invention can be observed using a transmission electron microscope. For example, after preparing a frozen section with a cryomicrotome, an electron stain in ruthenium tetroxide vapor can be observed with a transmission electron microscope at a magnification of about 2000 times.

  Moreover, it is preferable to add antioxidant to the resin composition of this invention. Preferred antioxidants include hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, amine antioxidants, etc., but one or more of these may be used in combination. can do. In particular, the combined use of a hindered phenolic antioxidant and another antioxidant is effective. Further, it is desirable to add a stabilizer such as a heat aging inhibitor, a copper damage inhibitor, an antistatic agent, a light resistance stabilizer, and an ultraviolet absorber. In particular, it is desirable to use a phenolic antioxidant containing a phosphorus atom in the molecule from the viewpoint of efficient radical capture. Furthermore, a crystal nucleating agent, a flame retardant, etc. can also be added.

  Examples of hindered phenolic antioxidants and stabilizers include 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tri (4-hydroxy). -2-methyl-5-tert-butylphenyl) butane, 1,1-bis (3-tert-butyl-6-methyl-4-hydroxyphenyl) butane, 3,5-bis (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3- (1,1-dimethylethyl) -4-hydroxy -5-methyl-benzenepropanoic acid, 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propio Roxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5′-di-t-butyl -4'-hydroxybenzyl) benzene, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate, N, N'-hexane-1,6diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ', 3 ", 5,5 '5 "-hexa-tert-butyl-a, a', a"-(mesitylene-2,4,6triyl) tri-p-cresol, diethyl [[3,5-bis [1,1-dimethylethyl -4-hydroxyphenyl] methyl] phosphate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2'3-bis [[3- [3,5-di-ter-butyl-4- Hydroxyphenyl] propionyl]] propionohydrazide, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2 , 4-8,10-tetraoxaspiro [5 · 5] undecane and the like.

  Examples of phosphorus antioxidants and stabilizers include 3,9-bis (p-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, tri (monononylphenyl) phosphite, triphenoxyphosphine, isodecyl Phosphite, isodecylphenyl phosphite, diphenyl 2-ethylhexyl phosphite, dinonylphenylbis (nonylphenyl) ester phosphoric acid, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5 t-butylphenyl) butane, tris (2,4-di-tert-butylphenyl) phosphite, pen Erythritol bis (2,4-di-tert-butylphenyl phosphite), 2,2′-methylene bis (4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, bis (2,6-di-tert) -Butyl-4-methylphenyl) pentaerythritol diphosphite, bis [2,4-bis [1,1-dimethylethyl] -6-methylphenyl] ethyl ester phosphorous acid, 6- [3- (3-tert- Butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] -dioxaphosphine, tetrakis (2,4 -Di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, bis (2,4-di-tert- Butylphenyl) pentaerythritol diphosphite, and the like.

Examples of sulfur-based antioxidants and stabilizers include 4,4′-thiobis [2-tert-butyl-5-methylphenol] bis [3- (dodecylthio) propionate], thiobis [2- (1,1-dimethylethyl). ) -5-methyl-4,1-phenylene] bis [3- (tetradecylthio) -propionate], pentaerythritol tetrakis (3-n-dodecylthiopropionate), bis (tridecyl) thiodipropionate, didodecyl -3,3'-thiodipropionate, dioctadecyl-3,3'-thiodipropionate, 4,6-bis (octylthiomethyl) -o-cresol, 4,4-thiobis (3-methyl-6) -Tert-butylphenol) and the like.
4,4′-bis (α, α-dimethylbenzyl) diphenylamine and 2 ′, 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] as amine antioxidants and stabilizers ] Propionyl]] propionohydrazide, N, N′-di-2naphthyl-p-phenylenediamine, N-phenyl-N′-4,4′-thiobis (2-t-butyl-5-methylphenol), 2 , 2-bis [3- (dodecylthio) propanoyloxymethyl] -1,3-propanediol bis [3- (dodecylthio) propionate] and the like.

  The addition amount of the antioxidant is preferably 0.1% by weight or more and 5% by weight or less based on the entire resin composition. If it is less than 0.1% by weight, the effect of preventing thermal deterioration may be poor. If it exceeds 5% by weight, the adhesion may be adversely affected.

  The resin composition of the present invention may contain a filler such as talc or mica, a pigment such as carbon black or titanium oxide, a flame retardant such as antimony trioxide or brominated polystyrene.

  A tackifier such as rosin and terpene can be blended in the resin composition of the present invention, which may improve the adhesion. As a compounding quantity, less than 40 weight% of the whole resin composition is desirable.

  The molded body of the present invention can be produced, for example, by placing a substrate on which electrical and electronic components are mounted in a mold and extruding the melt of the resin composition of the present invention into the mold. More specifically, for example, when a screw-type hot melt molding applicator is used, the resin composition is heated and melted at 160 to 280 ° C., and the molten resin composition is extruded and injected into a mold through a nozzle. Then, after a predetermined cooling time, the melt of the composition is solidified, and then the molded product is removed from the mold to obtain an encapsulated electrical / electronic component.

  Although it does not specifically limit as an applicator apparatus for hot-melt shaping | molding processes, For example, Nordson ST2 and semi-automatic hot-melt uniaxial extrusion molding machine EMC-18F9 by Imoto Seisakusho etc. are mentioned as a screw type. A generally used injection molding machine can also be used, but care must be taken to keep the injection pressure low so as not to damage the electrical and electronic parts to be sealed.

  When electrical and electronic parts are insert-molded using the resin composition of the present invention, the resin composition is melted to 280 ° C. or less using a heated screw and molded at a pressure of 20 MPa or less, but a low pressure of 10 MPa or less. It is desirable to form with the point that it is difficult to damage electronic parts. It is further desirable to mold at 240 ° C. or less and 5 MPa or less.

  When insert molding an electric / electronic component using the resin composition of the present invention, it is desirable to perform an easy adhesion surface treatment on the electric / electronic component in advance. By performing the easy adhesion surface treatment, the adhesive strength between the substrate and the resin composition can be further improved, and the waterproofness and the reliability of the electrical insulation can be improved.

  Examples of the easy adhesion surface treatment include flame treatment, silicon flame treatment, corona treatment, plasma treatment, UV irradiation, blast treatment, and primer treatment. Here, the silicon flame treatment refers to a surface treatment (so-called itro treatment) in which a surface treatment is performed with a flame obtained by burning a combustible gas containing a silicon compound. Among these easy adhesion surface treatments, silicon flame treatment and atmospheric pressure plasma treatment are preferable from the viewpoint of treatment effect and treatment cost.

<< Easy Adhesive Surface Treatment Method >>

<Silicon flame treatment>
Surface treatment of the adherend substrate was performed by silicon flame treatment using a T-LOC process apparatus manufactured by Time Auto Machine Co., Ltd.

(1) Cross-linked polyethylene-coated electric wire The PVC sheath of the cross-linked polyethylene-coated electric wire “600V CV” manufactured by Sumiden Hitachi Cable Co., Ltd. is peeled off to expose the cross-linked polyethylene-coated portion (6.3 mmφ) to a length of 50 mm. Cut and leave it on the treatment table, and use the T-LOC process device to surface the cross-linked polyethylene-coated electric wire.
・ Burner moving processing speed: 500 mm / sec ・ Burner and wire distance: 20 mm
-Number of treatments: Surface treatment was performed twice. Next, the cross-linked polyethylene-coated electric wire was rotated 90 ° clockwise along the circumference and similarly surface-treated.
Furthermore, after rotating 90 degrees right and performing the process, it rotated 90 degrees right again and processed.
As a result, the surface of the cross-linked polyethylene-coated electric wire was subjected to surface treatment a total of 8 times every 90 °.
(2) Polypropylene plate A commercially available polypropylene plate (manufactured by Mutual Riken Glass Manufacturing Co., Ltd., thickness: 2 mm) is cut into 20 mm × 100 mm, left on a processing table, and the surface of the polypropylene plate is attached to a T-LOC process device. make use of,
・ Burner moving processing speed: 500 mm / sec ・ Burner and wire distance: 20 mm
-Number of treatments: Surface treatment was performed twice.
(3) PBT plate In place of the polypropylene plate in (2) above, the surface treatment is performed in the same manner as in (2) above except that polybutylene terephthalate resin (EMC730 manufactured by Toyobo Co., Ltd.) containing 30% by mass of glass fiber is used. went.

<Atmospheric pressure plasma treatment>
Surface treatment of the adherend substrate was performed using Sekisui Chemical Co., Ltd. atmospheric pressure plasma surface treatment apparatus AP-T05-S320 type (remote head type).

(1) Cross-linked polyethylene-coated electric wire The PVC sheath of the cross-linked polyethylene-coated electric wire “600V CV” manufactured by Sumiden Hitachi Cable Co., Ltd. is peeled off to expose the cross-linked polyethylene-coated portion (6.3 mmφ) to a length of 50 mm. Cut and leave it on the treatment table, and use the atmospheric pressure plasma treatment device on the surface of this cross-linked polyethylene-coated wire,
・ Processing speed: 1000 mm / min ・ Distance between the top of the wire and the electrode: 2 mm
・ Treatment gas: Nitrogen gas only ・ Number of treatments: Surface treatment was performed once. Next, the cross-linked polyethylene-coated electric wire was rotated 90 ° clockwise along the circumference and similarly surface-treated.
Furthermore, after rotating 90 degrees right and performing the process, it rotated 90 degrees right again and processed.
As a result, the surface of the cross-linked polyethylene-coated electric wire was surface-treated four times in total every 90 °.
(2) Polypropylene plate Cut a commercially available polypropylene plate (thickness: 2 mm, manufactured by Mutual Rikagaku Glass Co., Ltd.) into 20 mm × 100 mm, and leave it on a processing table. make use of,
・ Processing speed: 1000 mm / min ・ Distance between the top of the wire and the electrode: 2 mm
・ Treatment gas: Nitrogen gas only ・ Number of treatments: Surface treatment was performed once.
(2) PBT plate In place of the polypropylene plate in (2) above, the surface treatment is performed in the same manner as in (2) above except that a polybutylene terephthalate resin (EMC730 manufactured by Toyobo Co., Ltd.) containing 30% by mass of glass fiber is used. went.
<< Evaluation Method for Resin, Resin Composition and Molded Body >>

<Measurement of melt viscosity>
Using a flow tester CFT-500C manufactured by Shimadzu Corporation
Test temperature: 200 ° C
Preheating time: 180 seconds Test weight: 10 kgf
Die hole diameter: 1mm
Die length: 10mm
The melt viscosity when the resin composition was extruded was measured.

<Measurement of melting point and glass transition temperature>
Using a differential scanning calorimeter “DSC220” manufactured by Seiko Denshi Kogyo Co., Ltd., put 5 mg of a sample into an aluminum pan, seal it with a lid, hold it at 220 ° C. for 5 minutes, and completely melt the sample. Then, it was quenched with liquid nitrogen, and then measured from -150 ° C. to 250 ° C. at a rate of temperature increase of 20 ° C./min. The inflection point temperature of the obtained curve was the glass transition temperature, and the endothermic peak temperature was the melting point.

<Formability evaluation>
A PVC sheath of a cross-linked polyethylene-coated electric wire “600V CV” manufactured by Sumiden Hitachi Cable Co., Ltd. is peeled off, and the cross-linked polyethylene-coated portion (6.3 mmφ) is exposed and cut to a length of 50 mm. Resin composition so that the cross-linked polyethylene-coated portion at one end of the electric wire has a cylindrical shape with a molded diameter of 10 mm, a contact length between the electric wire and the molding resin of 20 mm, and a length of only the molding resin of 30 mm The thing was shape | molded and the sealing body sample was obtained. A schematic diagram of a sealed sample is shown in FIG. The resin composition was molded using a semi-automatic hot-melt single-screw extruder EMC-18F9 manufactured by Imoto Seisakusho Co., Ltd. at 200 ° C., a molding pressure of 3 MPa, a holding pressure of 3 MPa, and a holding time of 10 seconds.
Evaluation criteria ○: Completely filled with no sink marks.
Δ: Filled without short shot, but there is a sink.
X: There is a short shot.

<180 ° bendability>
Using a mold made of aluminum that has been subjected to mold release treatment, using a semi-automatic hot melt single screw extruder EMC-18F9 manufactured by Imoto Seisakusho Co., Ltd. so that the size becomes 20 mm × 100 mm × 2 mm after molding, Molding was performed at a molding pressure of 3 MPa, a holding pressure of 3 MPa, and a holding time of 10 seconds.
When the obtained sample was folded 180 ° in two, whether or not a crack occurred in the bent portion was visually observed.

<Evaluation of adhesive strength>
(1) Pair-crosslinked polyethylene-coated electric wire Gripping A part and B part (see FIG. 1) of the sealed sample used for the above-described moldability evaluation, using Shimadzu Corporation tensile tester Autograph AG-IS By pulling up and down, the adhesive strength between the cross-linked polyethylene and the sealing resin composition was measured at a pulling rate of 50 mm / min in an environment of 23 ° C. and 60% Rh.
(2) Polypropylene plate A base material obtained by cutting a commercially available polypropylene plate (manufactured by Mutual Riken Glass Co., Ltd., thickness: 2 mm) into 20 mm x 100 mm is set in a mold, and the resin thickness after molding becomes 2 mm. Then, using a semi-automatic hot melt single screw extruder EMC-18F9 manufactured by Imoto Seisakusho Co., Ltd., molding was performed at 200 ° C., a molding pressure of 3 MPa, a holding pressure of 3 MPa, and a holding time of 10 seconds. The 90 ° peel strength of the obtained sample was measured using a tensile tester Autograph AG-IS manufactured by Shimadzu Corporation under an environment of 23 ° C. and 60% Rh at a pulling rate of 50 mm / min.
(3) Anti-PBT plate A sample was prepared in the same manner as in (2) above, except that a polybutylene terephthalate resin containing 30% by mass of glass fiber (EMC730 manufactured by Toyobo Co., Ltd.) was used instead of the polypropylene plate in (2) above. Prepared and measured the adhesive strength.

<< Example >>
In order to describe the present invention in more detail, examples and comparative examples are given below, but the present invention is not limited to the examples.

Production Example of Crystalline Copolyester (A) 166 parts by mass of terephthalic acid, 180 parts by mass of 1,4-butylene glycol, tetrabutyl titanate in a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation. 25 mass parts was added and esterification reaction was performed at 170-220 degreeC for 2 hours. After completion of the esterification reaction, 300 parts by mass of polytetramethylene glycol “PTMG1000” (Mitsubishi Chemical Co., Ltd.) having a number average molecular weight of 1000 and hindered phenol antioxidant “Irganox 1330” (manufactured by BASF Japan Ltd.) While 0.5 part by mass was added and the temperature was raised to 245 ° C., the pressure in the system was slowly reduced to 665 Pa at 245 ° C. over 60 minutes. Further, a polycondensation reaction was performed at 133 Pa or less for 60 minutes to obtain a polyester resin (A). The melting point of this polyester resin (A) was 160 ° C., and the melt viscosity at 200 ° C. was 28 Pa · s.

Production Example of Crystalline Copolyester (B), (C) In the same manner as in the above-mentioned crystalline copolyester (A), by changing the acid component or glycol component, the crystalline copolyester resin (B), ( C) was obtained. The properties of the resin are shown in Table 1.

TPA: terephthalic acid IPA: isophthalic acid AA: adipic acid
NDCA: 1,6-naphthalenedicarboxylic acid EG: ethylene glycol BD: 1,4-butylene glycol PTMG1000: polytetramethylene glycol (number average molecular weight 1000)
PTMG2000: polytetramethylene glycol (number average molecular weight 2000)

Production Example of Amorphous Copolyester (D) 83 parts by mass of terephthalic acid, 83 parts by mass of isophthalic acid, 50 parts by mass of ethylene glycol, neopentyl, in a reactor equipped with a stirrer, a thermometer, and a condenser for distillation 83 parts by weight of glycol and 0.25 parts by mass of tetrabutyl titanate were added, and an esterification reaction was performed at 170 to 220 ° C. for 2 hours. After completion of the esterification reaction, the temperature was raised to 230 ° C., while the pressure in the system was slowly reduced to 665 Pa at 230 ° C. over 60 minutes. Further, a polycondensation reaction was performed at 133 Pa or less for 30 minutes to obtain an amorphous polyester resin (D). The amorphous polyester resin (D) had a glass transition point of 60 ° C., a melt viscosity at 200 ° C. of 2 Pa · s, and no melting point was observed.

Production Example of Acid-Modified Polyolefin (a) 100 parts by mass of crystalline polypropylene, 15 parts by mass of maleic anhydride, 2 parts by mass of dicumyl peroxide and 150 parts by mass of toluene were put into an autoclave equipped with a stirrer and sealed. After performing nitrogen substitution for 5 minutes, the reaction was conducted at 140 ° C. for 5 hours with heating and stirring. After completion of the reaction, the reaction solution was poured into a large amount of methyl ethyl ketone to precipitate the resin. The precipitated resin was taken out, further washed several times with methyl ethyl ketone, and then dried to obtain an acid-modified polyolefin (melt viscosity at 200 ° C. = 3 Pa · s, acid addition amount 3.1 mass%).

Production Example of Acid-Modified Polyolefin (b) In the same manner as in the acid-modified polyolefin (a), the type of the polyolefin resin to be modified was changed to obtain an acid-modified polyolefin (b). Table 2 shows the composition and properties of each acid-modified polyolefin.

Polyolefin resin 1: crystalline propylene resin (weight average molecular weight 40,000)
Polyolefin resin 2: propylene-ethylene-butene (= 70/10/20 (molar ratio)) copolymer (weight average molecular weight 50,000)

Production Example 1 of Resin Composition
As crystalline polyester, 70 parts by mass of crystalline copolyester (A) and 30 parts by mass of crystalline copolyester (B), 10 parts by mass of amorphous copolyester (D) as an amorphous polymer, acid 20 parts by mass of modified olefin (a), 20 parts by mass of polypropylene Novatec PP BC08F manufactured by Nippon Polypro Co., Ltd. as olefins not acid-modified, 0.5 part by mass of IRGANOX 1010 manufactured by BASF Japan Ltd. as antioxidants, Sumitomo Chemical Co., Ltd. Sumitizer GP 0.5 parts by weight, as a colorant, Daiichi Seika Kogyo Co., Ltd. carbon black masterbatch PP-RM MK1510 0.5 parts by mass was added at 190 ° C. using a twin screw extruder. Resin composition 1 was obtained by melt-kneading.

Production Examples of Resin Compositions 2 to 10 Resin compositions 2 to 12 were obtained in the same manner as in Production Example of Resin Composition 1 according to the combinations in Table 3.

Polymer mainly composed of propylene chain P1: Novatec PP BC08F (polypropylene manufactured by Nippon Polypro Co., Ltd.)
Melt viscosity = 150Pa · s @ 200 ° C
Polymer with ethylene chain as main component E1: Sumikasen G808 (polyethylene manufactured by Sumitomo Chemical Co., Ltd.)
Melt viscosity = 29Pa · s @ 200 ° C
E2: Excellen VL EUL731 (Sumitomo Chemical Co., Ltd. special ethylene elastomer)
Melt viscosity = 640 Pa · s @ 200 ° C.
Epoxy resin: JER1007 (Mitsubishi Chemical Corporation bisphenol type epoxy resin) Melt viscosity = 10 Pa · s @ 200 ° C.
Stabilizer, etc. I-1010: IRGANOX 1010 (manufactured by BASF Japan Ltd.)
S-GP: Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.)
Colorant MK1510: PP-RM MK1510 (carbon black masterbatch manufactured by Dainichi Seika Kogyo Co., Ltd.)

Example 1
When the resin composition 1 was used as the resin composition for sealing and the semi-automatic hot-melt single-screw extruder EMC-18F9 manufactured by Imoto Seisakusho Co., Ltd. was used, the moldability evaluation for the crosslinked polyethylene coated electric wire was performed by the method described above. It was good with no shorts or sink marks. Further, when a 180 ° bending test was performed using the above-described method, no crack was generated and a good shape was maintained. Next, the adhesive strength between the crosslinked polyethylene of the sample subjected to the moldability evaluation and the resin composition was measured and found to be 200N. Table 4 shows the results of the measurement results of the adhesive strength with respect to the base material made of polypropylene and PBT, and the results when the base material subjected to the easy adhesion surface treatment was used.

Examples 2-6 and Comparative Examples 1-6
Table 4 shows the results of measuring the adhesive strength in the same manner as in Example 1 using Resin Compositions 2 to 6 and Comparative Resin Compositions 7 to 10 as the sealing resin composition.

Examples 1 to 6 satisfy the scope of the claims, and the moldability and 180 ° bendability are good, and the adhesion strength to crosslinked PE, PP, and PBT is good even without performing easy adhesion surface treatment. . And the adhesive strength is further improved by performing an easily bonding surface treatment.
On the other hand, in Comparative Example 1, the resin composition does not contain the amorphous resin, the acid-modified polyolefin, or the non-acid-modified polyolefin described in claim 1, and the melt viscosity is too high to be molded and bonded. The intensity could not be measured. Since Comparative Example 2 does not include an amorphous resin, an acid-modified polyolefin, or an unmodified polyolefin, it does not satisfy Claim 1 and has low adhesion to crosslinked PE or PP. Since Comparative Examples 3 and 5 do not contain an acid-modified polyolefin resin, they do not satisfy Claim 1, and when the easy adhesion surface treatment is not performed, the adhesion to crosslinked PE or PP is low. Since the comparative example 4 does not contain an amorphous resin, it does not satisfy claim 1, and when the easy adhesion surface treatment is not performed, the adhesion to the crosslinked PE or PP is low. Comparative Example 6 is mainly composed of an olefin resin and does not satisfy claim 1 and has good adhesion to crosslinked PE and PP, but has poor 180 ° bendability.

  The resin composition of the present invention is useful as a sealant for electric and electronic parts, and particularly useful as a waterproof and dustproof molding material for electric and electronic parts having complicated shapes, including a cross-linked polyethylene-coated electric wire and a polypropylene casing. is there. The sealed body sealed with the resin composition of the present invention is useful as a resin for sealing molding of, for example, various connectors for automobiles, communication, computers, home appliances, harnesses or electronic components, printed circuit boards, sensors, etc. It is.

11: Conductive wire 12: Cross-linked polyethylene coating 13: Sealing resin composition

Claims (14)

  3 to 18 parts by mass of a crystalline copolymer polyester, an amorphous resin, an acid-modified polyolefin, and a non-acid-modified polyolefin when the content of the crystalline copolymer polyester is 100 parts by mass. A resin composition that is an amorphous resin, 10 to 30 parts by mass of an acid-modified polyolefin, and 10 to 30 parts by mass of a polyolefin that is not acid-modified.   The resin composition according to claim 1, wherein the melt viscosity at 200 ° C is 100 Pa · s or less.   The resin composition according to claim 1, comprising at least two types of the crystalline copolyester.   The resin composition according to claim 1, wherein the crystalline copolyester has an ether bond and has a glass transition temperature of 0 ° C. or lower.   The resin composition according to claim 1, wherein the amorphous resin is an amorphous copolyester resin.   The resin composition according to claim 1, wherein the acid-modified polyolefin is acid-modified polypropylene.   The resin composition according to any one of claims 1 to 6, wherein the non-acid-modified polyolefin has an ethylene chain or a propylene chain as a main component.   8. The melt viscosity at 200 ° C. of each of the crystalline copolymerized polyester, the amorphous resin, the acid-modified polyolefin, and the non-acid-modified polyolefin is 200 Pa · s or less. 8. Resin composition.   The molded object using the resin composition in any one of Claims 1-8. The manufacturing method of the molded object which uses the resin composition in any one of Claims 1-8, and seals an electrical and electronic component by insert molding at the temperature of 20 MPa or less and the temperature of 280 degrees C or less. The method for producing a molded article according to claim 10, wherein the electric and electronic parts are subjected to an easy adhesion surface treatment. The method for producing a molded article according to claim 11, wherein the easy adhesion surface treatment is a plasma treatment or a flame treatment under atmospheric pressure. The method for producing a molded body according to claim 12, wherein the flame treatment uses a flame obtained by burning a silicon compound.   The molded object manufactured by the method in any one of Claims 10-13.