JP2007291371A - Mounding agent for model material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mounding agent for a model material with small dimensional increase by moisture absorption, solving problems in a conventional model material obtained by curing a displaying agent that the model deforms due to dimensional increase by moisture absorption, when using it as a master model or an inspection tool after a cutting process, and becomes useless as the inspection tool. <P>SOLUTION: This mounding agent for the model material comprises a polyol, a polyisocyanate, a hollow microsphere and a dehydrating agent, and further comprises a fluorine-containing water-repellent agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an overlay for a model material.

  Conventionally, as a model material placement agent, a placement agent comprising a polyol, a polyisocyanate, hollow microspheres, and a dehydrating agent is known (for example, see Patent Document 1).

JP 2003-160632 A

  However, in the model material made by curing the conventional placement agent, when used as a master model or inspection jig after cutting, the moisture in the air is adsorbed and the size increases by about 0.05% per year. There is a problem that the model is distorted or cannot be used as an inspection jig.

  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 includes a fluorine-containing water repellent (E) in a model material mounting agent comprising a polyol (A), a polyisocyanate (B), a hollow microsphere (C) and a dehydrating agent (D). A model material that is placed on a core material and cured; a model obtained by cutting the model material; and It is a manufacturing method of a model material characterized by mixing and discharging, placing on a core material, and hardening.

The overlay for model material of the present invention has the following effects.
(1) A model material having excellent dimensional stability during long-term storage is provided.
(2) A model obtained by cutting the model material has extremely small distortion and dimensional change due to moisture absorption.

Polyol (A) 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 (an 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) and polyester polyol (hereinafter abbreviated as PS polyol).

The polyhydric alcohol includes the following.
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, dipropylene 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, respectively) C6-10 alicyclic divalent alcohol [1,4-cyclohexanediol, cyclohexanedimethanol, etc.]; C8-20 aromatic ring-containing dihydric alcohol [xylylene glycol, bis ( Hydroxyethyl) benzene and the like];
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 referred to as GR, TMP respectively) , PE, SO and DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], saccharides and derivatives thereof such as sucrose, glucose, Fructose, mannose, lactose, and glycosides (such as methyl glucoside)];

Nitrogen-containing polyols (tertiary amino group-containing polyols and quaternary ammonium 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.] bishydroxyalkyl (C2-4 ) Compound [bis (2-hydroxyethyl) compound, bis (hydroxypropyl) compound and the like, for example, a tertiary nitrogen atom-containing polyol described in US Pat. No. 4,271,217], and their quaternized compounds [ The quaternizing agent or dialkyl carbon described in the above US patent specification (E.g., those having a C1-4 alkyl group such as dimethyl, diethyl and di-i-propyl carbonate). ) Quaternized product], for example, quaternary nitrogen atom-containing polyols described in the above-mentioned U.S. Patent Specification; and trivalent to octavalent or higher nitrogen-containing polyols such as trialkanol (C2-4) amine (triethanolamine) Etc.) and C2-12 aliphatic, cycloaliphatic, aromatic and heterocyclic polyamines [eg ethylenediamine, cyclohexanediamine, tolylenediamine, aminoethylpiperazine] polyhydroxyalkyl (C2-4) compounds [poly (2- Hydroxyethyl) compounds, bis (hydroxypropyl) compounds and the like [for example, tetrakis (2-hydroxypropyl) ethylenediamine, pentakis (2-hydroxypropyl) diethylenetriamine], and quaternized compounds similar to those described above.

Low molecular OH-terminated polymers include PT polyols, PS polyols and polyurethane (hereinafter abbreviated as PU) polyols having OH equivalents of less than 250, as described below. 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 polycondensation PS polyol and low mol lactone adduct of polyol [poly Condensates (for example, dihydroxyethyl adipate) of carboxylic acid and excess (1 mol per carboxyl group) polyhydric alcohol and EG caprolactone 1 mol adduct], and low-polymerization PU polyol [polyisocyanate (described below) PI It is.) And an excess (reaction products of polyhydric alcohols per isocyanate group 1 mol) (e.g. the reaction product of TDI 1 mol and EG2 mol described later) and the like.

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 abbreviated as EO, PO, BO, THF and MTHF), 1,3-propylene oxide, isoB
O, C5-12 α-olefin oxide, substituted AO, such as styrene oxide and epihalohydrin (such as epichlorohydrin), and combinations of two or more thereof (random addition and / or block addition) are included.

The polymeric polyol usually has an OH equivalent weight of 250 to 3,000 or more. The polyol usually has a number average molecular weight of 500 to 5,000 or more, preferably 700 to 4,500 (hereinafter abbreviated as Mn. Measurement is by gel permeation chromatography (GPC) method); Preferably 500 to 6,000, especially 700 to 4,000
It has a weight average molecular weight of 0 (hereinafter abbreviated as Mw. Measurement is based on GPC method). Examples include OH-terminated polymers [PT, PS, polyamide (hereinafter abbreviated as PD), PU, vinyl polymer (hereinafter abbreviated as VP) and polymer polyol (hereinafter abbreviated as P / P)], and 2 A mixture of seeds or more is included.
OH-terminated PT has a ring-opening polymer of AO, a structure in which one or more AOs are added to an initiator having at least two (2 to 8 or more) active hydrogen atoms PT polyols (AO adducts) having the above and PT polyols obtained by coupling two or more of them (same or different) with a coupling agent.

  Initiators for AO addition include, for example, polyhydric alcohols (described above), hydroxylamines, aminocarboxylic acids and hydroxycarboxylic acids; polyhydric phenols; and polycarboxylic acids (described below).

Hydroxylamine includes C2-10 (di) alkanolamines, cycloalkanolamines and alkylalkanolamines such as 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5- Aminopentanol, 6-aminohexanol, diethanolamine, di-n- and i-propanolamine, 3-aminomethyl-3,5,5-trimethylcyclohexanol, methylethanolamine and ethylethanolamine are included. Preference is given to 2-aminoethanol.

Aminocarboxylic acids include those having C2-12, such as amino acids [glycine, alanine, valine, (iso) leucine, phenylalanine, etc.], ω-aminoalkanoic acids (for example, ω-aminocapron, ω-aminoenanthate, ω-aminocapryl). , Ω-aminopergon, ω-
Aminocaprine, 11-aminoundecane and 12-aminododecanoic acid), and aromatic aminocarboxylic acids such as o-, m- and p-aminobenzoic acids.
Hydroxycarboxylic acids include those corresponding to the above aminocarboxylic acids (NH substituted with O) (for example, ω-hydroxycaproic acid, salicylic acid, p- and m-hydroxybenzoic acid), glycolic acid, glyceric acid, Tartronic acid, malic acid, tartaric acid and benzylic acid are included. Preference is given to 12-aminododecanoic acid.

  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, etc.), and condensed polycyclic dihydric phenols [dihydroxynaphthalene (eg, 1,5-dihydroxynaphthalene), binaphthol, etc.]; and trivalent to octavalent or higher Polyhydric phenols, such as monocyclic polyhydric phenols (pyrogallol, phloroglucinol, and mono- or dihydric phenols (phenol, cresol, xylenol, resorcinol, etc.) aldehydes or ketones (formaldehyde, glutaraldehyde, glyoxal) Acetone) Teichijimigobutsu (such as phenol or cresol novolak resins, intermediates resol, polyphenols obtained by condensation reaction of phenol with glyoxal or glutaraldehyde, and a polyphenol) obtained by condensation reaction of resorcin and acetone.

The addition of AO to the initiator can be carried out in the usual manner, and is carried out at atmospheric pressure in the absence of a catalyst or in the presence of a catalyst (alkali catalyst, amine catalyst, acidic catalyst, etc.) (particularly in the latter stage of AO addition). Alternatively, it is performed in one step or multiple steps under pressure. Two or more types of AO may be random addition, block addition, or a combination of both (for example, random addition followed by block addition).
AO adduct coupling agents include polyhalides such as C1-6 alkane polyhalides (eg C1-4 alkylene dihalides: methylene dichloride, 1,2-dibromoethane, etc.); epihalohydrins (eg epichlorohydrin, etc.); And polyepoxides.

Examples of OH-terminated PT include PT diols such as polyalkylene glycol (hereinafter abbreviated as PAG) [eg, PEG, PPG and PTMG, poly-3-methyltetramethylene ether glycol], copolymer polyoxyalkylene diol [EO / PO copolymerized diol, THF / EO copolymerized diol, THF / MTHF copolymerized diol and the like (weight ratio, for example, 1/9 to 9/1)], aromatic ring-containing polyoxyalkylene diol [polyoxyalkylene bisphenol A (bisphenol A) EO and / or PO adducts, etc.)]; and trifunctional or higher functional PT polyols such as polyoxypropylene triol (GR PO adducts, etc.); and one or more of these coupled with methylene dichloride It is.

The OH-terminated PS includes condensed PS polyol, polylactone (hereinafter abbreviated as PL) polyol, castor oil-based polyol [castor oil (ricinoleic acid triglyceride) and a modified polyol thereof), and polycarbonate polyol.
The condensed PS polyol is a polycondensation of a polyol and a polycarboxylic acid (refers to an acid or an ester-forming derivative thereof; the same shall apply hereinafter) (and a hydroxycarboxylic acid if necessary) or a reaction of the polyol with a polycarboxylic acid anhydride and AO. PL polyol is obtained by ring-opening addition of a lactone using a polyol as an initiator (or polycondensation of polyol and hydroxycarboxylic acid), a polyol modified product of castor oil is obtained by transesterification of castor oil and polyol, and polycarbonate. Polyol is a ring-opening addition / polycondensation of an alkylene carbonate using a polyol as an initiator, a polycondensation (transesterification) of a polyol and a diphenyl or dialkyl carbonate, or a polyol or a dihydric phenol (the above: bisphenol A, etc.) The Sugen reduction, can be produced.

The polyol used for the production of PS usually has an OH equivalent (Mn per OH) of 1,000 or less, preferably 30 to 500. Examples thereof include the above polyhydric alcohols [diols (eg, EG, 1,4-BD, NPG, HD and DEG) and trivalent or higher polyols (GR, TMP, PE, etc.)], the above PT polyols ( PEG, PPG, PTMG, etc.), and mixtures of two or more thereof. Preferred for the production of the condensed PS polyol is a combination of a diol and a small proportion (for example, 10 equivalent% or less) of a trivalent or higher polyol.

The polycarboxylic acid includes dicarboxylic acids and trivalent to tetravalent or higher polycarboxylic acids. Examples thereof include C2-30 or more (preferably C2-12) saturated and unsaturated aliphatic polycarboxylic acids, such as C2-15 dicarboxylic acids (eg, Shu, Aku, Maron, Adipine, Suberin, Azelain). , Sebatin, dodecanedicarboxylic, maleic, fumaric and itaconic acid), C6-20 tricarboxylic acids (eg tricarbaryl and hexanetricarboxylic acid)]; C8-15 aromatic polycarboxylic acids such as dicarboxylic acids (eg terephthalic, isophthalic and phthalic) Acid), tri- and tetra-carboxylic acids (e.g. trimellitic and pyromellitic acid); C6-40 alicyclic polycarboxylic acids (such as dimer acids); and sulfo group-containing polycarboxylic acids Introducing a group, such as sulfoscoha , Sulfomalone, sulfoglutar, sulfoadipine and sulfoisophthalic acid, and their salts (alkali metal, alkaline earth metal and group IIB metal salts, ammonium salts, amine salts, and quaternary ammonium salts, etc.)]; Polymer is included.

  Carboxy-terminated polymers include PT polycarboxylic acids such as carboxymethyl ethers of polyols [polyhydric alcohols, PT polyols etc. above] (obtained by reacting monochloroacetic acid in the presence of alkali); and PD, PS and / Or PU polycarboxylic acid, for example, polylactam polycarboxylic acid and PL polycarboxylic acid obtained by ring-opening polymerization of lactam or lactone (described above) using the above polycarboxylic acid as an initiator, or two or more of the above polycarboxylic acids A condensed PS polycarboxylic acid and a condensed PD polycarboxylic acid obtained by coupling (esterification or amidation) with a polyol (above), a polyamine (above) or a polyisocyanate (PI, described later), and the above polycarboxylic acids and Polyol and PI It was response (urethanization and esterification or amidation) include PU polycarboxylic acids comprising.

  Lactams are those of C4-15 (preferably C6-12), for example caprolactam, enantolactam, laurolactam and undecanolactam; lactones are those corresponding to the above lactams (NH is replaced by O) ( For example, ε-caprolactone, γ-butyrolactone, γ-valerolactone) is included.

Ester forming derivatives include acid anhydrides, lower alkyl (C1-4) esters and acid halides such as succinic, maleic, itacone and phthalic anhydride, dimethyl terephthalate, and malonyl dichloride.
Preferred for the production of the condensed PS polyol is a combination of a dicarboxylic acid and a small proportion (for example, 10 equivalent% or less) of a trivalent to tetravalent or higher polycarboxylic acid.
Lactones and hydroxycarboxylic acids include those listed above.
Alkylene carbonates include those having a C2-6 alkylene group, such as ethylene and propylene carbonate. Dialkyl carbonates include those having a C1-4 alkyl group, such as dimethyl, diethyl and di-i-propyl carbonate.

Specific examples of OH-terminated PS include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene / propylene adipate, polyethylene / butylene adipate, polybutylene / hexamethylene adipate, polydiethylene adipate, poly (polyethylene adipate) Ritetramethylene ether) adipate,
Polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol and polyhexamethylene carbonate diol are included.

The OH-terminated PD has a polycarboxylic acid (above) polycondensed with hydroxylamine (above) or polyol (above) and polyamine (PA) (above).
Ester) amide polyols are included.

The OH-terminated PU includes an OH-terminated urethane prepolymer obtained by modifying a polyol with PI. The polyol includes the above-mentioned polyhydric alcohol, polymer polyol (the above-mentioned OH-terminated PT and PS, and OH-terminated VP and P / P described later), and combinations of two or more thereof. Among the polyols, preferred are high-molecular polyols (especially OH-terminated PS and especially PT) and combinations thereof with low-molecular polyols (especially polyhydric alcohols). The amount of the low molecular polyol to be used in combination can be appropriately changed according to the required performance, but is generally 0.01 to 0.5 equivalent relative to 1 equivalent of the polymer polyol,
Furthermore, 0.02-0.4 equivalent, 0.1-0.2 equivalent is preferable.
In the production of the OH-terminated urethane prepolymer, the equivalent ratio of polyol to PI (OH / NCO ratio) is usually 1.1 / 1 to 10/1, preferably 1.4 / 1 to 4/1, particularly 1.4. /
1-2 / 1. The polyol and PI may be reacted in a single stage or in multiple stages (for example, after reacting a part of the polyol or PI, the remainder is reacted).

OH-terminated VPs include polybutadiene-based polyols such as OH-terminated butadiene homopolymers and copolymers (styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, etc.) [those having 1,2-vinyl structures, 1,4-trans structures. Having 1,4-cis structure, and having two or more of these (molar ratio of 1,2-vinyl / 1,4-trans / 1,4-cis 100-0 / 100-0 / 100 to 0, preferably 10 to 30/50 to 70/10 to 30], and hydrogenated products thereof (hydrogenation rate: for example, 20 to 100%); acrylic polyol, for example, acrylic copolymer [
Alkyl (C1-20) (meth) acrylate, or a copolymer of these and other monomers (styrene, acrylic acid, etc.)] with hydroxyl group introduced [hydroxyl group is mainly introduced with hydroxyethyl (meth) acrylate And partially saponified ethylene / vinyl acetate copolymers.

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). 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 polyols and PS polyols are preferable, AO adducts of polyhydric alcohols are more preferable, and AO adducts of dihydric to octahydric or higher polyhydric alcohols are particularly preferable. This is a combined use of an AO adduct of nitrogen-containing polyol.

In the polyisocyanate (B) in the present invention, the following polyisocyanate (PI) having 2 to 6 or more (preferably 2 to 3, particularly 2) isocyanate groups, and two or more of these A mixture is included.
(1) C (excluding carbon in the NCO group, the same shall apply hereinafter) 2 to 18 aliphatic PI:
Diisocyanates (hereinafter abbreviated as DI), such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / or 2,4 , 4-Trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-
Diisocyanatoethyl caproate, bis (2-isocyanatoethyl) fumarate and bis (2-isocyanatoethyl) carbonate;
Trifunctional or higher functional PI (such as triisocyanate), such as 1,6,11 1-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate and lysine ester triisocyanate (Phosgenation product of reaction product of lysine and alkanolamine, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2,6-diisocyanatohexa Noate);

(2) C4-15 alicyclic PI:
DI such as isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2 Dicarboxylates and 2,5- and / or 2,6-norbornane DI;
Trifunctional or higher functional PI (such as triisocyanate), such as bicycloheptane triisocyanate;
(3) C8-15 araliphatic PI:
m- and / or p-xylylene DI (XDI), diethylbenzene DI and α, α, α ′, α′-tetramethylxylylene DI (TMXDI);
(4) C6-20 aromatic PI:
DI, for example 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 (such as triisocyanate), for example, crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate);

(5) Modified form of PI:
Modified products of the above PI, such as modified products having carbodiimide, urethane, urea, isocyanurate, uretoimine, allophanate, biuret, oxazolidone and / or uretdione groups), such as urethane modified products such as MDI, TDI, HDI and IPDI (polyol and NCO-terminated urethane prepolymer obtained by reacting with excess PI), biuret modified product, isocyanurate modified product, trihydrocarbyl phosphate modified product, and mixtures thereof.
The polyol used for urethane modification includes the polyhydric alcohol, PT polyol and / or PS polyol. Preferred are polyols having an OH equivalent weight of 500 or less, particularly 30 to 200, such as glycols (EG, PG, DEG, DPG, etc.), triols (TMP, GR, etc.), tetrafunctional or higher functional polyols (PE, SO, etc.). ) And their AO (EO and / or P 2 O) (1-40 mol) adducts, in particular glycols and triols. The equivalent ratio of PI and polyol (NCO / OH ratio) in urethane modification is usually 1.1 / 1 to 10/1, preferably 1.4 / 1 to 4/1, particularly 1.4 / 1 to 2/1. It is.
The free isocyanate group content of the modified PI is usually 8 to 33%, preferably 10 to 30.
%, Particularly preferably 12 to 29%.

When forming a polyurethane resin from the polyol (A) and the polyisocyanate (B), when the ratio of (A) and (B) is represented by an isocyanate index [(equivalent ratio of NCO group / OH group) × 100] The index can be variously changed, but is preferably 80 to 140, more preferably 85 to 120, and particularly preferably 90 to 115 from the viewpoint of resin strength and ease of cutting of the model material.
As a reaction method of (A) and (B), even if it is a one-shot method, after reacting a part of (A) with (B) in advance to form an NCO-terminated prepolymer, the remaining ( A prepolymer method may be used in which a reaction is performed with A), or a part of (A) and (B) are reacted in advance to form an OH-terminated prepolymer, and then the remaining (B) is reacted. .

The hollow microsphere (C) is blended for the purpose of reducing the weight of the model material and improving the workability.
Examples of (C) include thermoplastic resins [one or more selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polymethyl (meth) acrylate, poly (meth) acrylonitrile, and copolymers thereof). And hollow microspheres made of a thermosetting resin (phenol resin, epoxy resin, urea resin, etc.) and an inorganic substance (glass, alumina, shirasu, carbon, etc.).
Among these, preferred are those made of thermoplastic resin, and more preferred are one or more selected from the group consisting of poly (meth) acrylonitrile, polymethyl (meth) acrylate and copolymers thereof.
The volume average particle size of (C) is preferably from 0.5 to 200 μm, more preferably from 1 to 150 μm, particularly from the viewpoint of fluidity and handleability of the composition and fineness of the polyurethane resin after curing. Preferably from 5 to 100 μm; the true specific gravity is preferably 0.005 to 0.1, more preferably 0.009 to 0.09, particularly preferably 0.00 from the viewpoints of handleability, fluidity of the composition and weight reduction. 015 to 0.08, most preferably 0.02 to 0.07.
Specific examples of (C) that can be obtained from the market include Expandel 551DE40d-42 and -60, Expandel 461DE-40d60 and -20d70, Expandel 092DE40d30 [all trade names, manufactured by Expandance Co., Ltd. Matsumoto Microsphere F-80ED and MFL series [Brand name, Matsumoto Yushi Seiyaku Co., Ltd.]; Phenolic microballoon BJO-0930 [Brand name, Union Carbide Corp.]; Scotchlite K-15 And -37 [both trade names, manufactured by Scotchlite Co., Ltd.] and the like.

  The amount of (C) used is usually 30% or less based on the total weight of (A) and (B). %, More preferably 4 to 20%.

(C) is usually contained on both the active hydrogen component (I) side and the isocyanate component (II) side comprising the polyol (A). If blended only on either the (I) side or the (II) side, the volume ratio of the two at the time of mixing greatly deviates from 1/1, resulting in poor workability and a limit to reducing the density. Moreover, the viscosity of the composition can be adjusted to the same level by distributing the blending amount of (C) necessary for the whole composition to each side of (A) and (B), and the mixing operation of both is facilitated. .
The distribution ratio is preferably 30 to 70% with respect to (A) and 70 to 30% with respect to (B) in the volume distribution ratio of (C). Within this range, the fluidity of (A) and (B) is close, and the mixing operation becomes easy.
In this case, in order to prevent the reaction between the moisture adsorbed on the surface of (C) and the polyisocyanate (B) during storage, a dehydrating agent (D) described later may be blended on the (II) side simultaneously.

The dehydrating agent (D) improves the adhesiveness by preventing the foaming phenomenon that occurs at the joint between the overlaying agents, or becomes a foaming agent in the urethanization reaction by mixing moisture and moisture into the overlaying agent. It is added for the purpose of preventing and densifying the surface when cutting the model material.
As (D), a commonly used compound having a dehydrating effect can be used, but a neutral or alkaline dehydrating agent is preferred.
Specific examples of (D) include calcium oxide, calcium sulfate (hemihydrate gypsum), calcium chloride, and molecular sieve.
Of these, calcium sulfate (hemihydrate gypsum), calcium chloride and molecular sieve are preferred from the viewpoint of the small volume average particle size in (D) and the fine dispersion in the composition and the stability of the dehydration effect. It is a molecular sieve.

The volume average particle size (μm) of (D) is preferably from 0.05 to 50, more preferably from 0.07 to 40, particularly preferably from the viewpoint of having a large surface area per unit weight and sufficient dehydration performance. It is 0.09-30, Most preferably, it is 0.1-20.
When using a molecular sieve, the pore size (nm) of the molecular sieve is preferably 1 to 100, more preferably 0.05 to 70, particularly preferably 0.1 to 50, most preferably from the viewpoint of efficient adsorption of water molecules. Preferably it is 0.2-40.
The amount of (D) used is usually 25% or less based on the total weight of (A) and (B), preferably from 0.3 to 20% from the viewpoint of dehydration effect and appropriate fluidity of the composition, Preferably it is 0.5 to 15%.

As the fluorine-containing water repellent (E), 1,000 to 1 × 10 7 Mn and 0.5 to 50
Those having a volume average particle diameter of 0 μm, for example, tetrafluoroethylene resin [trade name “Polyflon PTFE” (trade name abbreviation “PTFE”)], tetrafluoroethylene-perfluorovinyl ether copolymer [trade name “neoflon PFE” (Trade name abbreviation “PFE”)], tetrafluoroethylene-hexafluoropropylene copolymer (trade name abbreviation “FEP”), tetrafluoroethylene-ethylene copolymer (trade name abbreviation “ETFE”), Examples thereof include polyvinylidene fluoride (trade name abbreviation “PVDF”), ethylene trifluoride chloride resin (trade name abbreviation “PCTFE”), hexafluoropropylene resin (trade name abbreviation “HFP”), and mixtures thereof. Of these, "PTFE", "FEP" and "HFP" are preferable from the viewpoint of water repellency.

The amount of (E) used is preferably 0.01 to 15 based on the total weight of (A) to (D) from the viewpoint of the hygroscopicity of the model material, the fluidity of the composition and the mechanical strength of the model material. %, More preferably 0.05 to 13%, particularly preferably 0.1 to 10%.
The model material of the present invention formed from the active hydrogen component (I) composed of (A), (C) and (D) and the polyisocyanate component (II) is represented by (I) and / or (II) ( By including E), the dimensional stability of the model material can be improved. (E) may be contained in any of (I), (II) or a mixture of (I) and (II).

The overlaying agent of the present invention may be used in combination with other additives (F) as long as the effects of the present invention are not impaired.
(F) includes urethanization catalyst [amine catalyst (triethylenediamine, N-ethylmorpholine, diethylethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7, etc.), metal catalyst (octylic acid first Tin, dibutyltin dilaurate, lead octylate, etc.)]; plasticizer [xylene oligomer (condensate of mesitylene and formaldehyde, etc.), phthalate (dibutyl phthalate, dioctyl phthalate, dioctyl adipate, etc.), adipic acid di-2 -Ethylhexyl etc.]; thixotropic agent [particulate silica (volume average particle size 100 nm or less), hydrogenated castor oil, organic bentonite, etc.]; foam stabilizer (dimethylpolysiloxane having foam regulating effect, for example, main chain, side Chain and / or terminally terminated with a polyoxyalkylene chain, phenyl, alkyl, Non-reactive dimethylpolysiloxane modified with aralkyl or arylalkyl group, etc .; Filler [Inorganic filler (calcium carbonate, talc, aluminum hydroxide, mica, milled fiber, etc.), Organic filler (pulverization of thermosetting resin) Etc.), flame retardants, colorants (dyes, pigments, etc.), ultraviolet absorbers, anti-aging agents, antioxidants, antifungal agents, antibacterial agents and the like.

The total use amount of (F) is usually 50% or less, preferably 0.001 to 40, more preferably 0.05 to 35, and particularly preferably 0.00 based on the total weight of (A) and (B). 08-30.
The amount of each additive used in (F) is usually 1% or less, preferably 0.001 to 0.5%, based on the total weight of (A) and (B); Usually 25% or less, preferably 1 to 20%; a thixotropic agent is usually 15% or less, preferably 0.5 to 10%; a foam stabilizer is usually 6% or less, preferably 0.05 to 5 %; Filler is usually 45% or less, preferably 0.5 to 30%; Flame retardant is usually 30% or less, preferably 5 to 20%; Colorant, UV absorber, anti-aging agent, antioxidant The antifungal agent and the antibacterial agent are each usually 5% or less, preferably 0.01 to 3%.

As long as the placement agent of the present invention contains a polyol (A), a polyisocyanate (B), a hollow microsphere (C), a dehydrating agent (D), and a fluorine-containing water repellent (E), any The active hydrogen component (I) composed of (A), (C), (D) and (E) is preferable from the viewpoint of the reactivity between (A) and (B). , A two-component curable form with an isocyanate component (II) comprising (B), more preferably a two-component composition comprising (I) and (II) comprising (B), (C) and (D) It is curable.

The overlay of the present invention is produced by a method in which the above components are mixed using a propeller-type, bowl-type or other mixing tank with a stirring blade, a planetary mixer, or a Hobart mixer. In particular, when the proportion of the hollow microsphere (C) is large, the stirring share increases, and therefore it is preferable to use a planetary mixer.
As an example of an embodiment for producing the placement agent of the present invention, a production method using a planetary mixer will be described below.
(1) First, a liquid component [(A) in the active hydrogen component (I), and if necessary, a colorant (a liquid in which a colorant is dispersed in a dispersant), a plasticizer, a flame retardant, and the like, an isocyanate component (II) Then, (B) and, if necessary, a colorant (same as above), a plasticizer, a flame retardant, etc.] are put into a blending tank of a planetary mixer [for example, PLGM-400 type, manufactured by Inoue Seisakusho Co., Ltd.] 14 rpm, rotation 44 rpm) and mixing at room temperature (10-35 ° C.) for 10 minutes.
(2) Next, the powdered hollow microspheres (C) and other additives (F) are charged, and finally the dehydrating agent (D) is charged. After the addition, the mixture is mixed at low speed (above) and room temperature (above) for 10 to 30 minutes until the powder components become familiar with the liquid. After the powder component becomes familiar with the liquid, it is mixed for 30 minutes at room temperature at high speed (for example, revolution 21 rpm, rotation 66 rpm) while degassing under reduced pressure to -0.9 MPa or less. In order to further increase the smoothness of the surface of the model material after cutting, it is preferable to deaerate under reduced pressure during mixing to remove bubbles contained in the overlay.
(3) After mixing is completed, the mixing tank is set in a ram press type filling machine [for example, PHL-400 type, manufactured by Inoue Seisakusho Co., Ltd.] and filled into a 200 L straight drum can through a resin hose from the bottom tank of the mixing tank while applying pressure. To do.

When producing a model material of a desired shape using the placement agent of the present invention, a method of mixing and discharging the component (I) and the component (II) with a two-liquid discharger is preferable from the viewpoint of work efficiency. . As an example of a method for producing a model material using the placement agent, a placement process using a two-liquid dispenser will be described below.
(1) (I), (II) each in a pump part of a two-liquid discharger [for example, two-liquid mixing and discharging system, manufactured by Sakai Sangyo Co., Ltd.] having two pump parts that can suck and send liquid directly from the drum can. Set the drum filled with ingredients.
The pump type is preferably a plunger pump or a snake pump from the viewpoint that the paste-like material can be quantitatively fed, and more preferably, the hollow microsphere (C) is relatively less broken and has a low fluidity. However, it is a snake pump [for example, a drum can discharger 2NTL20 type, manufactured by Hyojin Equipment Co., Ltd.] capable of liquid feeding.
(2) Each pump liquid supply amount is set at such a ratio that the isocyanate index [(equivalent ratio of NCO group / OH group) × 100] is within the above range.
(3) A static mixer [e.g., static mixer 1.1 / 2-N30-131-F, manufactured by Noritake Co., Ltd.] is installed in the line to the discharge port, and two liquids are discharged. The mixed liquid mixed by the static mixer is placed on a core material [for example, rigid polyurethane foam Soflan board 80, manufactured by Axon Co., Ltd.] having a general target shape in advance.
(4) After standing at room temperature (10 to 35 ° C.) for 1 hour to perform primary curing, post curing at 50 to 70 ° C. for 8 to 12 hours to obtain a model material of a desired shape.

If the reaction rate of the present invention is increased, sufficient physical properties can be exhibited even at room temperature, but sufficient physical properties can be stably exhibited by heating and post-curing if necessary. The conditions for the post-curing are, from the viewpoint of completion of the urethanization reaction and work efficiency, from an industrial viewpoint, the curing temperature is preferably 40 to 100 ° C., more preferably 50 to 70 ° C., and the curing time is preferably 5 to 14 hours, Preferably it is 8 to 12 hours.

  The model (industrial model) of the present invention is obtained by cutting the obtained model material with an NC machine or the like. Since the cutting surface of the model of the present invention is finished smoothly, the model can be finished only by painting the surface once with sandpaper (for example, No. 240), and there is no need for regrinding and repainting.

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 represent parts by weight. The viscosity is a viscosity at 25 ° C. measured according to JIS K1557.
<Raw materials used>
Polyol (A11): Glycerin PO adduct, OH value 400 mg KOH / g
Polyether polyol of (shown), viscosity 0.38 Pa · s.
(A21): EO added to end of ethylenediamine PO adduct, OH number 450
Polyether polyol, weight ratio of EO and PO (EO / PO) 47.5
/52.5. Viscosity 1.15 Pa · s.

Polyisocyanate (B1): Crude MDI [trade name “Luprinate M-20S”, BA
SF Inoac Polyurethane Co., Ltd., viscosity 0.20 Pa · s, NC
O% is 31.4%]
Hollow microsphere (C1): Thermoplastic resin hollow microsphere [trade name “Expansel 551DE4
0d-42 ", manufactured by Expancel Co., Ltd., true specific gravity 0.042, volume average
Particle size 40μm]
Dehydrating agent (D1): Molecular sieve [trade name “Molecular sieve 3A-B powder
”, Manufactured by Union Showa Co., Ltd., volume average particle size 1 to 10 μm, pore size 30 nm
Less than]
Fluorine-containing water repellent (E1): tetrafluoroethylene resin [trade name "Polyflon PTFE M
-33 ", manufactured by Daikin Industries, Ltd., volume average particle size 300 μm]

Additive (F)
(F1) Plasticizer: Mesitylene-based xylene oligomer [trade name “NIKANOL
Y-51 ", manufactured by Fudou Co., Ltd., viscosity 0.05 Pa · s]
(F2) Thixotropic agent: particulate silica [trade name “AEROSIL 200”, JP
This Aerosil Co., Ltd. volume average particle size 12 nm].

Examples 1-7
After mixing each raw material into a planetary mixer [PLGM-400 type, manufactured by Inoue Seisakusho Co., Ltd.] with the blending composition (parts) shown in Table 1, the mixture was made uniform by revolving at 14 rpm and rotating at 44 rpm for 10 minutes. The mixture was stirred and degassed for 30 minutes at a revolution of 21 rpm, a rotation of 66 rpm, and −0.9 MPa or less to obtain a two-component curing type depositing agent composed of an active hydrogen component (I) and an isocyanate component (II). Each of the obtained components was filled in 100 L in two 200 L drums.
Next, the components (I) and (II) are fed at a total speed of 2 L / min with a snake pump (pail can discharger 2NTL20, manufactured by Hyojin Equipment Co., Ltd.) and sent by a Y-shaped tube. The liquid lines were combined into one, then mixed with a static mixer [1.1 / 2-N30-131-F type (30 elements), manufactured by Noritake Co., Ltd.] and discharged.
The inner dimension was set to a thickness of 30 mm in an aluminum mold having a width of 100 mm, a length of 1,000 mm and a height of 50 mm. After standing at 25 ° C. for 1 hour, it was cured by heating at 70 ° C. for 10 hours. This was allowed to cool for 8 hours and demolded to obtain a cured product of the overlay. The evaluation results of the cured product are shown in Table 1.

Comparative Example 1
A cured product was obtained in the same manner as in Examples 1 to 7 with the blending composition (parts) shown in Table 1. The evaluation results of the cured product are shown in Table 1.

Evaluation of dimensional stability was performed as follows.
NC machine [NCE23-1H type router, manufactured by Kikukawa Iron Works Co., Ltd.] was cut so that the cured product had a height of 25 mm to obtain a cured product having a width of about 100 mm, a length of about 1,000 mm, and a height of 25 mm. . The weight of the cured product was divided by the volume calculated from the product of the lengths of the three sides to obtain the density.
The cured product is stored in a room of constant temperature and humidity (23 ° C., relative humidity 55%, the same shall apply hereinafter), and then a three-dimensional measuring machine [BHN710, manufactured by Mitutoyo Corporation] is used in the room of constant temperature and humidity. The length of the cured product was measured over time.
When the cured product is stored in a constant temperature and humidity room, the length change rate (%) after 3, 6 and 12 months has elapsed in the constant temperature and humidity room with reference to the length (a) after 24 hours. It calculated | required by the following formula.

Length change rate (%) = (b−a) × 100 / a

[Where a is a reference length and b is a length after a predetermined period]

  From the results of Table 1, it can be seen that the molded articles of the examples are extremely superior in dimensional stability during long-term storage compared to those of the comparative examples.

  Since the model obtained by cutting the model material obtained by curing the model material placement agent of the present invention is extremely small in distortion and dimensional change due to moisture absorption, the placement agent is used for models such as design models and master models. A model widely used as a cutting material or the like and obtained is extremely useful because it can be used for, for example, a full-scale model of a railway vehicle, an automobile, and a home appliance, an interior model of an automobile, and the like.

Claims (7)

The overlay for a model material comprising a polyol (A), a polyisocyanate (B), a hollow microsphere (C) and a dehydrating agent (D) is characterized by containing a fluorine-containing water repellent (E). Model material overlay. The overlay according to claim 1, wherein the content of (E) is 0.01 to 15% based on the total weight of (A) to (D). The overlaying agent is an active hydrogen component (I) comprising a polyol (A), hollow microspheres (C), a dehydrating agent (D) and a fluorine-containing water repellent (E), and an isocyanate component comprising a polyisocyanate (B) ( The placement agent according to claim 1 or 2, which is a two-component curing type placement agent comprising II). A model material obtained by placing and curing the placement agent according to claim 1 on a core material. A model formed by cutting the model material according to claim 4. A method for producing a model material, wherein the placement agent according to claim 3 is mixed and discharged by a two-liquid discharger, placed on a core material, and cured. In a model material formed from an active hydrogen component (I) comprising a polyol (A), hollow microspheres (C) and a dehydrating agent (D), and a polyisocyanate component (II), (I) and / or (II ) Containing a fluorine-containing water repellent (E). A method for improving the dimensional stability of the model material.