JP2010155942A - Composition for forming material for making model by cutting - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the existing problem that conventional materials for making models by cutting is not enough in overall heat radiation during molding thereof, hence a large temperature difference between inner part and other parts of a molded article generates internal strain, thus cutting of the molded article after radiation results in shape change. <P>SOLUTION: The composition for forming material for making models by cutting includes a reaction curing component (A), comprised of a polyurethane resin or an epoxy resin, and a heat conductive filler (B) having a thermal conductivity of 10-600 W/mK, and the model is made by cutting the composition for forming material for making models. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a model material forming composition for cutting. More specifically, the present invention relates to a model material-forming composition for cutting that provides a model material with small internal strain and excellent dimensional stability.

  Conventionally, as a model material, a foamed polyurethane molded product obtained by foaming a mixture of natural wood, a bisphenol alkylene oxide adduct, an aliphatic polyol, an aromatic polyisocyanate and a dehydrating agent by a mechanical floss method (so-called A polyurethane resin molded product for cutting called synthetic wood) is used (for example, see Patent Document 1).

JP-A-6-329747

  However, with the above conventional materials, the overall heat dissipation during molding is not sufficient, and internal distortion occurs due to a large temperature difference between the inside of the molded product and the other parts, and when the molded product after heat dissipation is cut There was a problem of deformation.

  The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention comprises a reaction curable component (A) that forms a polyurethane resin or an epoxy resin, and a thermally conductive filler (B) having a thermal conductivity of 10 to 600 W / mK. A model material forming composition for cutting; a model material obtained by reaction-curing and molding the composition; and a model obtained by cutting the model material.

The model material forming composition for cutting according to the present invention has the following effects.
(1) There is no generation of scorch during molding of the composition.
(2) A model material formed by molding the composition is excellent in dimensional stability.
(3) Excellent shape stability of the model.

[Reactive curable component (A)]
The reaction curable component (A) in the present invention includes a polyurethane resin-forming component (A1) or an epoxy resin-forming component (A2).

[Polyurethane resin forming component (A1)]
The polyurethane resin-forming component (A1) includes polyol (A1a) and polyisocyanate (A1b).

Polyol (A1a) is a divalent to octavalent or higher polymer polyol [having an OH equivalent of 250 or more (based on OH value, molecular weight per OH)], a low molecular polyol (OH equivalent of less than 250) And mixtures of two or more thereof.
Low molecular polyols include polyhydric alcohols and low molecular OH-terminated polymers [polyether polyol (hereinafter abbreviated as PT polyol), polyester polyol (hereinafter abbreviated as PS polyol), etc.].

The polyhydric alcohol includes the following (1) to (3).
(1) Dihydric alcohol [carbon number (hereinafter abbreviated as C) 2-20 or more), for example, C2-12 aliphatic dihydric alcohol [(di) alkylene glycol such as ethylene glycol, diethylene glycol, propylene glycol, di Propylene glycol, 1,2-, 2,3-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter EG, DEG, PG, DPG, BD, HD, NPG and MPD), dodecanediol, etc.]; C6-10 alicyclic divalent alcohol [1,4-cyclohexanediol, cyclohexanedimethanol, etc.]; C8-20 aromatic ring-containing 2 Hydric alcohol [xylylene glycol, bis (hydroxyethyl) benzene ];

(2) Trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol (hereinafter, respectively) GR, TMP, PE, SO and DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], sugars and their derivatives [eg sucrose Glucose, fructose, mannose, lactose, and glycosides (such as methyl glucoside)];

(3) Nitrogen-containing polyols (tertiary amino group-containing polyols): Nitrogen-containing diols such as C1-12 aliphatic, alicyclic and aromatic ring-containing primary monoamines [methylamine, ethylamine, 1- and 2-propylamine , Hexylamine, 1,3-dimethylbutylamine, 1-, 2- and 3-aminoheptane, dodecylamine, cyclopropylamine, cyclohexylamine, aniline, benzylamine, etc.]; and bishydroxyalkyl (C2-4) compounds; Trivalent to octavalent or higher nitrogen-containing polyols such as trialkanol (C2-4) amines (such as triethanolamine) and C2-12 aliphatic, alicyclic, aromatic and heterocyclic polyamines [eg ethylenediamine, Cyclohexanediamine, tolylenediamine, aminoethyl pipette Jin] polyhydroxy alkyl (C2-4) halide or the like.

Low molecular weight OH-terminated polymers have an OH equivalent of less than 250 and include polyether polyols, polyester polyols, and the like.
For example, a low-polymerization alkylene oxide (hereinafter abbreviated as AO) ring-opening polymer and a low-mol AO adduct of an active hydrogen atom-containing polyfunctional compound [for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (hereinafter referred to as PEG respectively) , PPG, PTMG), etc., bis (hydroxyethoxy) benzene and bisphenol A ethylene oxide (hereinafter abbreviated as EO) 2 to 4 mol adduct], low-condensation condensation polyester polyol and polyol low-mol lactone adduct [poly Condensates (for example, dihydroxyethyl adipate) of carboxylic acid and excess (1 mol per carboxyl group) polyhydric alcohol and 1 mol of caprolactone of EG.

AO includes C2-12 or more (preferably C2-4) AO such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran and 3 -Methyl-tetrahydrofuran (hereinafter each EO
, PO, BO, THF and MTHF), 1,3-propylene oxide, isoBO
, C5-12 α-olefin oxides, substituted AOs such as styrene oxide and epihalohydrins (such as epichlorohydrin), and combinations of two or more thereof (random addition and / or block addition).

The polymeric polyol usually has an OH equivalent weight of 250 to 3,000 or more. The polyol is usually 500 to 5,000 or more, preferably 700 to 4,500.
Number average molecular weight [hereinafter abbreviated as Mn. The measurement is gel permeation chromatography (G
PC) method. ].
Examples include OH-terminated polymers [PT polyols, PS polyols and polymer polyols (hereinafter abbreviated as P / P)], and mixtures of two or more thereof.
The OH-terminated PT polyol includes a ring-opening polymer of AO, an initiator having at least two (2 to 8 or more) active hydrogen atoms [polyhydric alcohol (described above), hydroxylamine, polyvalent Phenol and polycarboxylic acid etc.] include PT polyol (AO adduct) having a structure in which one or more AOs are added.

Hydroxylamines include C2-10, (di) alkanolamines, cycloalkanolamines and alkylalkanolamines.

The polyhydric phenol includes C6-18 dihydric phenol such as monocyclic dihydric phenol (hydroquinone, catechol, resorcinol, urushiol, etc.), bisphenol (bisphenol A, F, C, B, AD and S, dihydroxybiphenyl, 4,4′-dihydroxydiphenyl-2,2-butane and the like), and condensed polycyclic dihydric phenol [dihydroxynaphthalene (eg, 1,5-dihydroxynaphthalene), binaphthol and the like];
Octavalent or higher polyhydric phenols such as monocyclic polyphenols (pyrogallol, phloroglucinol, and mono- or dihydric phenols (phenol, cresol, xylenol, resorcinol, etc.) aldehydes or ketones (formaldehyde, glutaraldehyde) , Glyoxal, acetone) low condensates (eg phenol or cresol novolac resin, intermediate of resole, polyphenol obtained by condensation reaction of phenol and glyoxal or glutaraldehyde, and polyphenol obtained by condensation reaction of resorcin and acetone) It is.

  Examples of OH-terminated PT polyols include polyether diols such as polyalkylene glycols (eg, PEG, PPG and PTMG); and tri- or higher functional polyether polyols such as polyoxypropylene triol (eg, PO adduct of GR). included.

  The OH-terminated PS polyol includes a condensed polyester polyol, a polylactone (hereinafter abbreviated as PL) polyol, a castor oil-based polyol [castor oil (ricinoleic acid triglyceride) and a modified polyol thereof), and a polycarbonate polyol.

The polymer polyol (P / P) is obtained by in situ polymerization of an ethylenically unsaturated monomer in a polyol (previously OH-terminated PT and / or PS, or a mixture thereof with the polyhydric alcohol). It is done. Ethylenically unsaturated monomers include acrylic monomers such as (meth) acrylonitrile and alkyl (C1-20 or higher) (meth) acrylate (such as methyl methacrylate); hydrocarbon (hereinafter abbreviated as HC) monomers such as aromatic Unsaturated HC (such as styrene) and aliphatic unsaturated HC (C2-20 or higher alkenes, alkadienes, such as α-olefins and butadiene); and combinations of two or more thereof (for example, combined use of acrylonitrile / styrene) (Weight ratio 100/0 to 80/20)]. P / P has a polymer content of, for example, 5 to 80% or more, preferably 30 to 70%.
Among the above polymer polyols, PT polyol is preferable.

  The OH number of the polyol (A1a) (unit is mgKOH / g. In the following, only the numerical value is shown) is preferably 200 to 1, from the viewpoint of heat resistance of the cured product, mechanical strength and scorch suppression due to heat generation during curing. 000, more preferably 250 to 600, particularly preferably 300 to 500.

  As the polyisocyanate (hereinafter abbreviated as PI) (A1b), those conventionally used for polyurethane can be used. Examples thereof include aromatic PI, aliphatic PI, alicyclic PI, araliphatic PI, and modified products of these PIs described in Japanese Patent No. 2618804 and Japanese Patent No. 2928918.

The aromatic PI includes 6 to 20 carbon atoms (hereinafter abbreviated as C) (excluding carbon in the NCO group, the same shall apply hereinafter), such as diisocyanate (hereinafter abbreviated as DI) [1,3-and / or 1,4- Phenylene DI, 2,4- and / or 2,6-tolylene DI (TDI), 4, 4'- and / or 2,4'-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane and 1,5-naphthylene DI ];
Trifunctional or higher functional PI (triisocyanate, etc.) [crude TDI, crude MDI (polymethylene polyphenyl polyisocyanate), etc.].

Aliphatic PIs include C2-18, such as DI [ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / or Or 2,4,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate and bis (2- Isocyanatoethyl) carbonate];
Trifunctional or higher functional PI (such as triisocyanate) [1,6,1 1-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate and lysine ester triisocyanate ( Phosgenates of reaction products of lysine and alkanolamines), 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2,6-diisocyanatohexa Noate etc.].

As alicyclic PI, C4-15, for example, DI [isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI, bis (2-isocyanato] Ethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane DI etc.];
Trifunctional or higher functional PI (triisocyanate etc.) [bicycloheptane triisocyanate etc.] can be mentioned.

  The araliphatic PI includes C8-15, such as m- and / or p-xylylene DI (XDI), diethylbenzene DI and α, α, α ', α'-tetramethylxylylene DI (TMXDI).

  Examples of modified products of PI include modified products having a carbodiimide, urethane, urea, isocyanurate, uretoimine, allophanate, biuret, oxazolidone and / or uretdione group), such as urethane-modified products such as MDI, TDI, HDI and IPDI (described above). NCO-terminated urethane prepolymers obtained by reacting an excess of PI with a polyether polyol, etc.), biuret modified products, isocyanurate modified products, trihydrocarbyl phosphate modified products, and mixtures thereof.

  In the polyurethane resin-forming component (A1) in the present invention, the ratio of the polyol (A1a) and the polyisocyanate (A1b) can be variously changed, but from the viewpoint of the mechanical strength and cutting workability of the cured product, the isocyanate index is preferable. [(NCO group / active hydrogen atom-containing group equivalent ratio) × 100], 80 to 140, more preferably 85 to 120, and particularly preferably 90 to 115.

[Epoxy resin component (A2)]
The epoxy resin component (A2) is composed of a polyepoxide (A2a) having two or more epoxy groups in one molecule and a curing agent (A2b) [polyamine curing agent (A2b1) or acid anhydride curing agent (A2b2)]. Become. Examples of the polyepoxide (A2a) include polyglycidyl ether and polyglycidyl ester.

  Polyglycidyl ethers include epihalohydrins (such as epichlorohydrin) or dihalohydrins (such as glyceryl dichlorohydrin) and C6-50 or higher polyvalent (divalent to hexavalent or higher) phenols [eg, bisphenol A and -F 1,1-bis (4-hydroxyphenyl) ethane, resorcinol, hydroquinone, catechol, and their nuclear substitutes, halides], or C2-100 polyvalent (divalent to hexavalent or higher) alcohols [ For example, alkane polyol [ethylene glycol, propanediol, 1,4-butanediol, trimethylolpropan, glycerin, pentaerythritol (hereinafter abbreviated as EG, PG, 1,4-BD, TMP, GR, PE), number average Molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. ] 3,000 or less polyalkylene (alkylene group is C2-4) glycol [for example, those obtained by reaction with diethylene glycol (hereinafter abbreviated as DEG), triethylene glycol, tetraethylene glycol, polyethylene glycol], etc. It is done.

  Polyglycidyl esters include epihalohydrins (e.g. epichlorohydrin) or dihalohydrins (e.g. glycerin dichlorohydrin) and C6-20 or higher divalent to hexavalent or higher aliphatic or aromatic polycarboxylic acids (e.g. And oxalic acid, fumaric acid, maleic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid and their halides).

  Of these polyepoxides (A2a), polyglycidyl ethers of polyhydric phenols are preferable from the viewpoint of toughness and strength of reaction-cured trees, and bisphenol A and -F, 1,1-bis (4-hydroxyphenyl) are more preferable. ) Glycidyl ether of ethane.

  As polyamine curing agent (A2b1), C2-18 aliphatic polyamine, C4-15 alicyclic ring-containing polyamine, C6-20 aromatic ring-containing polyamine, C4-15 heterocyclic ring-containing polyamine, Mn200-2,000 Polyamide polyamine etc. are mentioned.

  Examples of the aliphatic polyamine include C2-6 alkylenediamine (for example, ethylenediamine, propylenediamine, tetramethylenediamine), C4 to 36 poly (2-6) alkylene (alkylene group is C2-6) polyamine [for example, diethylenetriamine. , Triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobispropylamine, bis (hexamethylene) triamine], their alkyl (alkyl group is C1-4) or hydroxyalkyl (hydroxyalkyl group is C2-4) Substituents [for example, dialkyl (alkyl group is C1-4) aminopropylamine, diethylaminopropylamine, aminoethylethanolamine], diethylene glycol bispropylenediamine, and the like.

  Examples of the alicyclic-containing polyamine include isophoronediamine and bis (4-amino-3-methylcyclohexyl) methane.

  Examples of the aromatic ring-containing polyamine include aromatic polyamines (metaphenylenediamine, diaminodiphenylmethane, etc.) and araliphatic polyamines (eg, metaxylenediamine).

  Examples of the heterocyclic-containing polyamine include N-aminoethylpiperazine.

  Polyamide polyamines include dimer acid (C36-54) [polymerized fatty acid of C36 produced by heat polymerization of unsaturated fatty acid (C18-24) mainly composed of linoleic acid or oleic acid in the presence of a catalyst. And those obtained by reacting an excess (2 moles or more per mole of acid) with a polyamine (the above-mentioned alkylene diamine, polyalkylene polyamine, etc.).

  Examples of the acid anhydride curing agent (A2b2) include aromatic ring-containing acid anhydrides [C8-24, such as phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimethylate). Meritate), pyromellitic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride], aliphatic acid anhydride [C4 or more and weight average molecular weight (hereinafter abbreviated as Mw), measured by GPC method. .) 2,000 or less, for example, maleic anhydride, succinic anhydride, alkenyl succinic anhydride having an alkenyl group of C8-12, polyadipic anhydride (Mw 750-850), poly azelaic anhydride (Mw 1,200-1) , 300), polysebacic anhydride (Mw1,600-1,700)], alicyclic acid anhydride [C8-20, for example, Torahidoro phthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl cyclohexene tetracarboxylic anhydride include methylnadic anhydride.

  Among these curing agents (A2b), a polyamine curing agent (A2b1) is preferable from the viewpoint that primary curing at room temperature (20 to 35 ° C.) is possible, and a C2-18 aliphatic is more preferable. It is a polyamine.

  The amount of these curing agents (A2b1) or (A2b2) used for the polyepoxide (A2a) is preferably 0 with respect to 1 equivalent of the epoxy of (A2a) from the viewpoint of mechanical strength and heat resistance of the reaction-cured resin. .25 to 2.0 (more preferably 0.5 to 1.75) is an amount that is equivalent to a curing agent.

[Thermal conductive filler (B)]
The thermally conductive filler (B) has a thermal conductivity (W / mK) of 10 to 600 (preferably 50 to 500). If the thermal conductivity is less than 10, scorch is likely to occur due to deterioration of heat dissipation during molding, and those exceeding 600 are difficult to obtain industrially.
(B) includes carbon fiber, carbide (silicon carbide, boron carbide, etc.), nitride (silicon nitride, aluminum nitride, boron nitride, etc.), metal oxide (alumina, etc.), metal (silver, copper, aluminum, etc.) Powder etc. are mentioned.
Among these, carbon fiber, metal powder, and metal oxide are preferable from the viewpoint of heat dissipation during molding of the composition and from an industrial viewpoint, and carbon fiber, copper powder, and alumina are more preferable.

[Model material forming composition for cutting]
The model material forming composition for cutting according to the present invention contains the reaction curable component (A) and the heat conductive filler (B), and the weight ratio of (A) to (B) is the composition. From the viewpoint of moldability of the product and heat dissipation during molding, it is preferably 20/80 to 80/20, more preferably 30/70 to 70/30.

  If necessary, the model material forming composition for cutting according to the present invention may further include a microballoon (C1), a plasticizer (C2), a filler (C3), a lubricant (C4), a foam stabilizer (C5), You may contain the at least 1 sort (s) of additive (C) chosen from the group which consists of a foaming agent (C6), a dehydrating agent (C7), and a catalyst (C8).

Examples of the microballoon (C1) include those made of synthetic resin (thermoplastic resin and thermosetting resin) and inorganic material (such as shirasu balloon and glass balloon).
Examples of the thermoplastic resin include a copolymer of two or more ethylenically unsaturated monomers selected from the group consisting of (meth) acrylonitrile, methyl (meth) acrylate, vinyl chloride, and vinylidene chloride; the thermosetting resin Examples thereof include phenol resin, epoxy resin and urea resin.

  Examples of commercially available (C1) made of thermoplastic resin include Expandel 551DE40d4 and -40d60, Expandel 461DE40d60 and -20d70, Expandel 092DE40d30 [all manufactured by Expandance Co., Ltd.], and Matsumoto Microsphere F. -80ED and MFL series [both manufactured by Matsumoto Yushi Seiyaku Co., Ltd.] and the like; as commercially available (C1) made of glass, Scotchlite C15 and K37 [both manufactured by Sumitomo 3M Limited], and Cellstar Z-27 And Z-36 [both manufactured by Asahi Glass Co., Ltd.] and the like.

The volume average particle size (μm) of (C1) is preferably 0.5 to 120, more preferably 1 to 100, and particularly preferably 5 to 90 from the viewpoint of the smoothness of the cut surface of the cured product.
The true specific gravity of (C1) is preferably from 0.005 to 0.5, more preferably from 0.01 to 0.45, particularly preferably from 0.015 to 0.40, from the viewpoints of handleability and weight reduction of the cured product. It is. Here, the true specific gravity is a value measured using a pycnometer [trade name “Acupic 1330”, manufactured by Micromeritex Co., Ltd.].

Examples of the plasticizer (C2) include phthalic acid esters (dibutyl phthalate, dioctyl phthalate, etc.), adipic acid esters (dioctyl adipate, etc.), phosphoric acid triesters (triisopropylphenyl phosphate, etc.);
Examples of the filler (C3) include inorganic fillers (calcium carbonate, talc, aluminum hydroxide, mica, milled fiber, etc.) and organic fillers (thermosetting resin pulverized product, etc.);
As the lubricant (C4), fatty acid amides (C6-60, for example, fatty acid primary amide, N-carbyl fatty acid primary amide, N, N-dicarbyl fatty acid primary amide, N, N′-substituted fatty acid amide, polyamine fatty acid Amide), metal soaps [C22-34 higher fatty acid metal (aluminum, calcium, magnesium, barium, zinc, etc.) salts, etc.] and the like.
Examples of the foam stabilizer (C5) include silicone foam stabilizers (such as organopolysiloxane);
Examples of antifoaming agents (C6) include silicone antifoaming agents (organopolysiloxane, etc.);
Examples of the dehydrating agent (C7) include calcium oxide, calcium sulfate (hemihydrate gypsum), calcium chloride, molecular sieve and the like;
Examples of the catalyst (C8) include amine catalysts (such as triethylenediamine) and metal catalysts (such as dibutyltin laurate).

  The amount used based on the total weight of the composition is usually 40% or less for the microballoon (C1), preferably from 0.01 to 30%, more preferably from the viewpoint of cutting workability and liquid feed quantitativeness by the composition pump. 0.05 to 20%, particularly preferably 0.1 to 10%; plasticizer (C2) and filler (C3) are each usually 15% or less, preferably 5 to 10%; lubricant (C4), dehydrating agent (C7) is usually 10% or less, preferably 2 to 8%; foam stabilizer (C5) is usually 5% or less, preferably 0.1 to 3%; (C6) is usually 3% or less, Preferably it is 0.5 to 2%; (C8) is 0.5% or less normally, Preferably it is 0.008 to 0.2%.

The composition of the present invention is used in the form of a two-component curable type comprising a main agent (I) and a curing agent (II). The component of the main component (I) includes the polyol (A1a) in the polyurethane resin-forming component (A1) and the polyepoxide (A2a) in the epoxy resin-forming component (A2). Further, the component of the curing agent (II) includes a polyisocyanate (A1b) in the (A1) and a curing agent (A2b) in the (A2).
Accordingly, the form includes a curing agent comprising (A1a) or (A2a), and if necessary, a main agent (I) comprising an additive (C), (A1b) or (A2b), and optionally an additive (C). A combination with (II) is included, and the thermally conductive filler (B) may be blended in either the main agent (I) and / or the curing agent (II).

  The composition of the present invention comprises, for example, each component of the main agent (I) or the curing agent (II), a mixing tank provided with a propeller type, vertical type or other uniaxial rotation type stirring blade, and a biaxial rotation and planetary type Mixer [manufactured by Inoue Mfg. Co., Ltd., PLGM-400, the same applies hereinafter. ] Etc. are used for mixing. In particular, when the blending ratio of the microballoon (C1) is large, it is preferable to use a planetary mixer because the stirring share increases.

[Model material]
The model material of the present invention is manufactured by reaction-curing and molding the composition. That is, a model material having a desired shape can be obtained by mixing and discharging the main agent (I) liquid and the curing agent (II) liquid into a mold by using a two-liquid mixing and discharging machine. Here, the mixing ratio (weight ratio) of the liquid (I) and the liquid (II) is preferably 0.5 / 1 to 1 / 0.3 from the viewpoint of mixing efficiency.

The example of a manufacturing process of the model raw material using the composition of this invention is shown below.
(1) A container filled with the liquids (I) and (II) is set in a two-liquid mixing and discharging machine capable of feeding the liquids of the main agent (I) and the curing agent (II). These (I) and (II) liquids are plunger pumps [for example, Tooling-Mix PH200fix type, manufactured by Taiyo Techno Co., Ltd.] or snake pumps [Discharger for pail cans 2NTL20 type, manufactured by Hyojin Equipment Co., Ltd.] Etc. can be used for liquid feeding.
(2) The pumping amounts are set so that the liquids (I) and (II) are in a predetermined ratio.
(3) Install a static mixer (trade name “Static Mixer” 11 / 2-N30-131-F, manufactured by Noritake Co., Ltd.) in the line up to the discharge port. Discharge and mold.
(4) After primary curing at room temperature (20 to 35 ° C.), curing is performed at 50 to 70 ° C. for 8 to 12 hours to obtain a model material having a desired shape.

Since the model material of the present invention contains the filler (B) excellent in thermal conductivity, it has the characteristics that the temperature difference between the inside of the molded product and other parts is small and the internal strain is small. The linear expansion coefficient (× 10 ⁻⁶ / ° C.) of the model material of the present invention is preferably 40 or less, more preferably 25 or less, particularly preferably 10 or less, from the viewpoint of suppressing distortion and deformation of the model. The linear expansion coefficient can be reduced by selecting the type of filler (B) and increasing the amount of the filler used. Here, the linear expansion coefficient is measured by a method described later according to JIS K7197.

  The model (industrial model or the like) of the present invention can be manufactured by cutting the model material with an NC machine or the like.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following, “parts” represents parts by weight.

The composition and symbols of the raw materials used in Examples and Comparative Examples are as follows.
Polyol (A1a-1): glycerin PO adduct, polyether polyol having an OH number of 400
[Product name "Sanix GP400""Sanyo Chemical Industry Co., Ltd."]
Polyisocyanate (A1b-1): Crude MDI [trade name “Millionate MR-200”, manufactured by Nippon Polyurethane Industry Co., Ltd.]
Polyepoxide (A2a-1): Bisphenol A type polyepoxide [trade name “Epicor
828 ", manufactured by Japan Epoxy Resin Co., Ltd.]
Polyepoxide (A2a-2): 1,4 butanediol diglycidyl ether [trade name "
Epositor 750 ", manufactured by Air Products Japan Ltd.]
Polyamine (A2b-1): Diethylene glycol diaminopropyl ether [Product
Name “Ancamin 1922”, Air Products Japan Ltd.]
Thermally conductive filler (B-1): carbon fiber [trade name “XNG-90”, thermal conductivity 500 W /
mK, average fiber length 3.6 mm, manufactured by Nippon Graphite Fiber Co., Ltd.]
Thermally conductive filler (B-2): Copper powder [trade name “MA-CH—S”, thermal conductivity 398 W / m
K, volume average particle size 10 μm, density 5.2 g / cm ³ , manufactured by Mitsui Kinzoku Co., Ltd.]
Thermally conductive filler (B-3): Alumina [trade name “AKP-20”, thermal conductivity 25 W / m
K, volume average particle size 0.5 μm, density 1.3 g / cm ³ , manufactured by Sumitomo Chemical Co., Ltd.
]
Microballoon (C1-1): Acrylic microballoon [trade name “Matsumoto Micro
Sphere MFL-80GCA ”, volume average particle size 20 μm, density 0.24
g / cm ³ , manufactured by Matsumoto Yushi Seiyaku Co., Ltd.]
Filler (C3-1): Calcium carbonate [trade name “Whiteon SB”, thermal conductivity 0.6 W /
mK, manufactured by Shiraishi Calcium Co., Ltd.]
Antifoaming agent (C6-1): Silicon antifoaming agent [trade name “SAG-47”, manufactured by Nippon Unicar Co., Ltd.
]
Dehydrating agent (C7-1): synthetic zeolite [trade name “PURMOL3”, CU Chemie
Made by Ueticon AG]
Catalyst (C8-1): Di-n-butyltin dilaurate [trade name “Stan BL”, Sankyo
Organic Synthesis Co., Ltd.]

Example 1 [Polyurethane resin model material]
In accordance with the composition shown in Table 1, each component of the main agent (I-1) was put into a planetary mixer, stirred for 10 minutes at 130 rpm, then stirred for 5 minutes under a reduced pressure of 30 mmHg or less, defoamed and the main agent (I-1 ) (Polyol component) was obtained.
On the other hand, each component of the curing agent (II-1) is blended in a separate blending container, stirred at 130 rpm, stirred for 5 minutes under a reduced pressure of 30 mmHg or less, and defoamed to obtain curing agent (II-1) Ingredient) was obtained. Next, (II-1) is put into a planetary mixer so that (I-1) and (II-1) have a predetermined mixing ratio, and the mixture is stirred at 130 rpm for 5 minutes under a reduced pressure of 30 mmHg or less. It was poured into a mold of length × width × height = 200 × 50 × 50 mm and cured by heating at 80 ° C. for 2 hours. Thereafter, the mold was allowed to stand at room temperature (25 ° C.) for 8 hours and removed from the mold to obtain a model material (1). About the obtained model raw material (1), performance evaluation was performed by the below-mentioned test. The results are shown in Table 1.

Examples 2-7, Comparative Examples 1-3 [Polyurethane resin model material]
Model materials (2) to (7) in Examples 2 to 7 and model materials (Ratio 1) to (Ratio 3) in Comparative Examples 1 to 3 with the composition shown in Table 1 in the same manner as Example 1. ), The performance of these was similarly evaluated. The results are shown in Table 1.

Example 8 [epoxy resin model material]
Main components (I-8) (polyepoxide component) and curing agents (II-8) (polyamine component) were obtained in the same manner as in Example 1 with the composition shown in Table 2. Next, (II-8) is added to (I-8) in the planetary mixer so that (I-8) and (II-8) have a predetermined blending ratio. The mixture was mixed, poured into a mold, and primary cured at 20 to 25 ° C. for 16 hours. Thereafter, the mold was allowed to stand at 50 to 55 ° C. for 10 hours to be secondarily cured, and then further left at room temperature (25 ° C.) for 8 hours, followed by demolding to obtain a model material (8). About the obtained model raw material (8), performance evaluation was performed similarly to Example 1. FIG. The results are shown in Table 2.

Examples 9-14, Comparative Examples 4-6 [Epoxy resin model material]
Model materials (9) to (14) of Examples 9 to 14 and model materials (Ratio 4) to (Ratio 6) of Comparative Examples 4 to 6 with the composition shown in Table 2 in the same manner as Example 8. ), The performance of these was similarly evaluated. The results are shown in Table 2.

<Performance evaluation test of model material>
(1) Density (Unit: g / cm ³ )
The demolded model material was conditioned at 25 ° C. and 55% RH for 12 hours, the weight of the test piece was measured, and the value divided by the volume of the test piece was taken as the density of the model material.
(2) Scorch A model material (vertical x horizontal x height = 200 x 50 x 50 mm, the same applies hereinafter) is cut at the center, and the cross-section is observed to scorch (resin burn phenomenon due to reaction heat. Resin browning) The occurrence and the extent of occurrence) were evaluated according to the following criteria.
<Evaluation criteria>
○ No scorch generation (no resin discoloration)
△ Scorch slightly generated (slightly browned)
× Scorch generation (Dark brown color change)

(3) Linear expansion coefficient (unit: / ° C) [Evaluation of dimensional stability]
After conditioning for 12 hours at 25 ° C. and 55% RH, three test pieces each cut at a length × width × thickness = 10 × 5 × 5 mm from one end and center of a rectangular parallelepiped model material Using a linear expansion coefficient measuring instrument [model name “TMA / SS6100”, manufactured by SII Co., Ltd.], the measurement was performed according to JIS K7197. Measure dimensional change at 25-80 ° C., measure average dimensional change rate per 1 ° C. at 30-60 ° C. for each test piece, and further determine the number average value for each of the three end portions and three central portions. This was made into the linear expansion coefficient of each part.
(4) Strain (unit: mm) [Evaluation of shape stability]
A test piece cut out from a model material at length x width x thickness = 200 x 25 x 25 mm was conditioned for 12 hours at 50 ° C and 55% RH, and then the cut surface was placed under an atmosphere of 25 ° C and 55% RH. And placed on a surface plate. Five minutes later, the maximum value of the gap between the test piece and the surface plate where the central portion was raised in an arcuate shape was read with a gap gauge in units of 0.1 mm, and the obtained value was defined as strain.

  From the results in Tables 1 and 2, the model material forming composition for cutting according to the present invention has no scorch during molding, and the model material formed by molding the composition has dimensional stability compared to the comparative one. It can be seen that a model formed by cutting the model material is excellent in shape stability (distortion).

  The model material formed by reacting and curing the model material-forming composition for cutting according to the present invention is excellent in dimensional stability, and the model formed by cutting the model material has less distortion. It is extremely useful because it can be used widely as a model such as a master model, a simple injection mold, a cutting material such as an inspection jig, and the like.

Claims (6)

Formation of a cutting model material comprising a reactive curable component (A) for forming a polyurethane resin or an epoxy resin and a thermally conductive filler (B) having a thermal conductivity of 10 to 600 W / mK Sex composition. The composition according to claim 1, wherein the weight ratio of (A) to (B) is 20/80 to 80/20. The composition according to claim 1 or 2, further comprising at least one additive selected from the group consisting of microballoons, plasticizers, fillers, lubricants, foam stabilizers, antifoaming agents and dehydrating agents. A model material obtained by reaction-curing and molding the composition according to claim 1. The model material according to claim 4, having a linear expansion coefficient of 40 × 10 ⁻⁶ / ° C. or less. A model obtained by cutting the model material according to claim 4 or 5.