JP4153482B2 - Model material overlay - Google Patents

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 (Patent Document 1).
JP 2003-160632 A

However, in recent years, the cutting speed has been increasing faster in order to shorten the work period in cutting large models. The conventional overlay for model materials has a problem in that if the cutting is performed at a high speed, the cutting surface is crushed and fluffed, and a finishing process is required as a subsequent process.
That is, an object of the present invention is to provide a placement material for a model material in which the surface can be cut smoothly even in high-speed cutting, and a finishing process is unnecessary.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the feature of the model material placement agent of the present invention is that the model material placement agent comprising polyol (A), organic polyisocyanate (B), hollow microsphere (C) and dehydrating agent (D) has a melting point (JIS). The gist is that K0064-1992, 3.2 melting point test method) contains an organic lubricant (W) composed of a fatty acid amide of polyamine having a temperature of 50 to 90 ° C.

The overlay for the model material of the present invention is extremely unlikely to cause “sagure” or “fluff” even when high-speed cutting is performed. Therefore, a finishing process becomes unnecessary.
Therefore, the placement material for model material of the present invention is particularly suitable for a full-scale model of an automobile, for example, because a large model having a large cutting area can be cut in a short period of time.

The melting point (° C.) of the organic lubricant (W) in the present invention is usually 50 to 90, preferably 51 to 88, more preferably 52 to 86, and particularly preferably 53 to 85. That is, the lower limit of the melting point (° C.) of (W) is preferably 50, more preferably 51, particularly preferably 52, and most preferably 53. Similarly, the upper limit is preferably 90, more preferably 88, Particularly preferred is 86, and most preferred is 85. Within this range, the smoothness of the surface after curing becomes even better.
In addition, melting | fusing point (degreeC) is the value measured based on 3.2 melting | fusing point measuring method of JISK0064-1992.

  Examples of the organic lubricant (W) having a melting point of 50 to 90 ° C. include fatty acid amide (W1), fatty acid ester (W2), petroleum wax (W3), and natural wax (W4).

As fatty acid amide (W1), fatty acid primary amide (ww1), N-alkyl fatty acid primary amide (ww2) and N, N-dialkyl fatty acid primary amide (ww3), polyamine fatty acid amide (ww4), etc. are used. it can.
As (ww1), an unsaturated fatty acid amide having 18 to 22 carbon atoms or the like is used.
Examples of the unsaturated fatty acid amide include oleic acid amide, linoleic acid amide, linolenic acid amide, erucic acid amide, and ricinoleic acid amide.
(Ww2) is a saturated fatty acid amide having 10 to 16 carbon atoms of a saturated hydrocarbon monosubstituted amine having 1 to 18 carbon atoms, or a saturated fatty acid amide having 16 to 18 carbon atoms of an unsaturated hydrocarbon monosubstituted amine having 18 carbon atoms. And unsaturated fatty acid amides having 18 to 22 carbon atoms of saturated hydrocarbon monosubstituted amines having 18 carbon atoms.

  Examples of saturated fatty acid amides having 10 to 16 carbon atoms of saturated hydrocarbon monosubstituted amines having 1 to 18 carbon atoms include N-methyl capric acid amide, N-methyl lauric acid amide, N-methyl myristic acid amide, and N-dodecyl laurin. Examples include acid amides. Examples of the saturated fatty acid amide having 16 to 18 carbon atoms of the unsaturated hydrocarbon monosubstituted amine having 18 carbon atoms include N-oleyl palmitic acid amide and N-oleyl stearic acid amide. Examples of the unsaturated fatty acid amide having 18 to 22 carbon atoms of the saturated hydrocarbon monosubstituted amine having 18 carbon atoms include N-stearyl oleic acid amide and N-stearyl erucic acid amide.

  (Ww3) is a saturated fatty acid amide having 10 to 16 carbon atoms of a saturated hydrocarbon disubstituted amine having 1 to 18 carbon atoms, a saturated fatty acid amide having 16 to 18 carbon atoms of an unsaturated hydrocarbon disubstituted amine having 18 carbon atoms, And an unsaturated fatty acid amide having 18 to 22 carbon atoms of a saturated hydrocarbon disubstituted amine having 18 carbon atoms.

Examples of saturated fatty acid amides having 10 to 16 carbon atoms of saturated hydrocarbon disubstituted amines having 1 to 18 carbon atoms include N, N-dimethylcapric acid amide, N, N-dimethyllauric acid amide, and N, N-dimethylmyristic acid. Amide, N, N-dimethylpalmitic acid amide, N, N-didodecyllauric acid amide, N, N-didodecylmyristic acid amide, N, N-didodecylpalmitic acid amide and N, N-didodecylstearic acid amide Etc.
Examples of the saturated fatty acid amide having 16 to 18 carbon atoms of the unsaturated hydrocarbon disubstituted amine having 18 carbon atoms include N, N-dioleyl palmitic acid amide and N, N-dioleyl stearic acid amide. Examples of the unsaturated fatty acid amide having 18 to 22 carbon atoms of the saturated hydrocarbon disubstituted amine having 18 carbon atoms include N, N-distearyl oleic acid amide and N, N-distearyl erucic acid amide.

Examples of the polyamine fatty acid amide (ww4) include polyamides obtained by condensation reaction of polyamines with aliphatic monocarboxylic acids and / or aliphatic polyvalent carboxylic acids.
Examples of the polyamine include alkylene diamines having 2 to 6 carbon atoms (for example, ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.), polyalkylene polyamines having an alkylene group having 2 to 6 carbon atoms ( Examples thereof include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Examples of the aliphatic monocarboxylic acid include linear or branched fatty acids having 2 to 32 carbon atoms such as butanoic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, palmitic acid, stearin. Examples include acids, isostearic acid, isoarachidic acid, acrylic acid, oleic acid, erucic acid and the like. Examples of the polycarboxylic acid include aliphatic dicarboxylic acids having 2 to 40 carbon atoms (for example, malonic acid, succinic acid, adipic acid, elaidic acid, maleic acid, fumaric acid, 3,3-dimethylpentanedioic acid, etc.), carbon Examples thereof include aliphatic polyvalent carboxylic acids of 4 to 42 (for example, 3,3-dimethyl-5-ethyloctane-1,2,8-tricarboxylic acid, etc.) and dimer acids of the above unsaturated fatty acids.

  Specific examples of (ww4) include fatty acid amides obtained by condensation reaction of aliphatic monocarboxylic acids having 16 to 22 carbon atoms and polyethylene polyamine, alkylene diamines having 2 to 4 carbon atoms and unsaturated compounds having 16 to 22 carbon atoms. Fatty acid amide obtained by condensation reaction with aliphatic monocarboxylic acid and obtained by condensation reaction of aliphatic dicarboxylic acid or dimer acid having 6 to 54 carbon atoms with polyethylene polyamine and aliphatic monocarboxylic acid having 16 to 32 carbon atoms And amide compounds.

Examples of the fatty acid ester (W2) include a monohydroxy fatty acid ester having 18 carbon atoms and a glycerin fatty acid ester.
Examples of the ester of a monohydroxy fatty acid having 18 carbon atoms include methyl 12-hydroxystearate, stearyl 12-hydroxystearate, ethylene glycol mono-12-hydroxystearate and propylene glycol mono-12-hydroxystearate.
Examples of the glycerin fatty acid ester include glyceryl mono-stearate and glyceryl mono-behenate.

  As the petroleum wax (W3), a paraffin wax having 20 to 50 carbon atoms (tetracosane, pentacosane, hexacosane, etc.) and the like can be used.

  As the natural wax (W4), plant wax (such as carnauba wax and candelilla wax), animal wax (such as beeswax) and mineral wax (such as ozokerite) can be used.

  Of these organic lubricants (W), fatty acid amide (W1), petroleum wax (W3), and natural wax (W4) are preferable, and the smoothness of the surface after curing and the difficulty of repelling the paint when painting a model. From the viewpoint of the above, fatty acid amide (W1) is more preferable, and from the viewpoint of viscosity stability of the mounting agent, N, N-dialkyl fatty acid primary amide (ww1) and polyamine fatty acid amide (ww4) are particularly preferable.

  As the polyol (A), the organic polyisocyanate (B), the hollow microsphere (C) and the dehydrating agent (D), the same ones as those known (Patent Document 1 etc.) can be used. Moreover, another additive (E) can be included as needed, and the same thing as a well-known thing etc. can be used as another additive (E).

Of the known polyols (A), polyhydric alcohol alkylene oxide adducts and / or polyhydric phenol alkylene oxide adducts (A1) and amine alkylene oxide adducts (A2) are preferred, and more preferred are polyhydric alcohol alkylene oxides. It is a polyol composed of an adduct and / or a polyhydric phenol alkylene oxide adduct (A1) and an amine alkylene oxide adduct (A2).
Examples of the polyhydric alcohol include divalent alcohols having 2 to 20 carbon atoms (alkylene glycols such as ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; and Cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol), trivalent alcohols having 3 to 20 carbon atoms (alkanetriols such as glycerin, trimethylolpropane, trimethylolethane and hexanetriol); 4 having 5 to 20 carbon atoms To 8-valent polyhydric alcohols (intramolecular dehydration of alkane polyols such as pentaerythritol, sorbitol, mannitol and sorbitan, intermolecular dehydration of alkane polyols such as diglycerin and dipentaerythritol; and Sugar, glucose, mannose, fructose and sugar and their derivatives such as methyl glucoside); and the like.

  Examples of the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A, bisphenol F and bisphenol sulfone; and condensates (novolak resins) of phenol and formaldehyde.

  Examples of amines include ammonia; aliphatic amines {alkanolamines having 2 to 20 carbon atoms (monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, etc.), alkylamines having 1 to 20 carbon atoms (n-butylamine, octylamine, etc.) ), C2-C6 alkylenediamine (ethylenediamine, propylenediamine, hexamethylenediamine, etc.), C4-C20 polyalkylenepolyamine [alkylene polyamine having a C2-C6 alkylene group (diethylenetriamine and dihexylene) Triamine, etc.), and a trialkylene polyamine having 2 to 6 carbon atoms in the alkylene group (such as triethylenetetramine and trihexylenetetramine), tetraethylenepentamine, pentaethylenehexamine, etc.]} C6-C20 aromatic mono- or poly-amine (aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline, diphenyletherdiamine, etc.); C4-C20 alicyclic Amines (isophoronediamine, cyclohexylenediamine, dicyclohexylmethanediamine, etc.); and C4-C20 heterocyclic amines (piperazine, aminoethylpiperazine, heterocyclic amines described in JP-B No. 55-21044, etc.), etc. Is mentioned.

  The alkylene oxide is preferably an alkylene oxide having 2 to 8 carbon atoms, more preferably ethylene oxide (EO), propylene oxide (PO), 1,2-, 1,4-, 1,3- or 2,3- Butylene oxide, styrene oxide and a mixture of two or more thereof (block, random and / or a mixture thereof), particularly preferably PO and EO. In the case of PO and / or EO, other alkylene oxides may be included, but when other alkylene oxides are used, the amount used (% by weight) is 10 or less based on the weight of PO and EO. preferable.

  Preferable specific examples of the polyether polyol include PO adducts of glycerin, trimethylolpropane, pentaerythritol, sucrose, triethanolamine, ethylenediamine and diethylenetriamine.

As the polyol (A), other commonly used polyols other than these can also be used, for example, compounds other than the above (polycarboxylic acid and phosphoric acid) containing at least 2 (preferably 2 to 8) active hydrogens. Polyester polyol; diene polyol such as polybutadiene polyol and hydrogenated product thereof; hydroxyl group-containing vinyl polymer such as acrylic polyol; natural oil polyol such as castor oil; modification of natural oil polyol Thing; The said polyhydric alcohol etc. are mentioned.
When these other polyols are used, the amount used (% by weight) is preferably 30 or less, more preferably 20 or less, based on the weight of the polyol (A).

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (such as succinic acid, adipic acid, sebacic acid, glutaric acid and azelaic acid); and aromatic polycarboxylic acids having 8 to 18 carbon atoms (terephthalic acid). And isophthalic acid).

  Examples of the polyester polyol include the polyhydric alcohol and / or polyol (A1), the polycarboxylic acid or its anhydride, and an ester-forming derivative (anhydrous) such as a lower alkyl (carbon number of alkyl group: 1 to 4) ester. A condensation reaction product with maleic acid, phthalic anhydride, dimethyl terephthalate, etc.) or a condensation reaction product with the carboxylic acid anhydride and alkylene oxide; an addition reaction of alkyleonoxide (EO, PO, etc.) of the condensation reaction product A polylactone polyol, for example, obtained by ring-opening polymerization of a lactone (e.g., ε-caprolactone) using the polyhydric alcohol as an initiator; a polycarbonate polyol, for example, a reaction product of the polyhydric alcohol and an alkylene carbonate; Is mentioned.

2-10 are preferable, as for the number (piece) of the hydroxyl group which a polyol (A) has, More preferably, it is 3-8, Most preferably, it is 3-6, Most preferably, it is 3-4. Within this range, the strength and impact resistance after curing are further improved.
The hydroxyl value (mgKOH / g) of the polyol (A) is preferably 200 to 700, more preferably 250 to 650, particularly preferably 300 to 600, and most preferably 350 to 550. Within this range, the strength and toughness after curing are further improved.

  When the polyol (A) comprises a polyhydric alcohol alkylene oxide adduct and / or a polyhydric phenol alkylene oxide adduct (A1) and an amine alkylene oxide adduct (A2), it is based on the total weight of (A1) and (A2). The content (% by weight) of (A1) is preferably 60 to 99, more preferably 65 to 98, particularly preferably 70 to 96, most preferably 75 to 95, and the content of (A2) (Wt%) is preferably from 1 to 40, more preferably from 2 to 35, particularly preferably from 4 to 30, and most preferably from 5 to 25. Since (A2) has higher reactivity with the organic polyisocyanate (B) than (A1), the urethanization reaction can be started without using the catalyst usually used for the urethanization reaction, and the catalyst was used. It is possible to prevent the foaming phenomenon due to the reaction between moisture and the organic polyisocyanate (B). Therefore, in this range, the smoothness and fineness of the surface after curing are further improved.

  The content (% by weight) of N atom in the polyol (A) is preferably from 0.01 to 10, more preferably from 0.03 to 8, particularly preferably from 0.05 to 8, based on the weight of (A). 6, most preferably 0.1-5. Within this range, the smoothness of the surface after curing, the fineness of the texture, and the like are further improved, as is the content of (A2).

  Among known organic polyisocyanates (B), aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (carbodiimide modification, allophanate modification, urea modification, burette modification) , Isocyanurate-modified or oxazolidone-modified), isocyanate group-terminated prepolymers, and mixtures of two or more thereof, more preferably aromatic polyisocyanates, modified aromatic polyisocyanates, aromatic polyisocyanate-terminated prepolymers. A polymer and a mixture of two or more thereof, particularly preferably an aromatic polyisocyanate, a carbodiimide-modified product of an aromatic polyisocyanate, an aromatic polyisocyanate group-terminated prepolymer and a mixture of two or more of these, Phenyl isocyanate-terminated prepolymers and mixtures of two or more of them - also preferably polymethylene polyphenyl isocyanate, methylene - bis - phenyl isocyanate, methylene - bis - carbodiimide modified product of phenyl isocyanate, methylene - bis.

As the aromatic polyisocyanate, aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), aromatic triisocyanates having 6 to 20 carbon atoms, and crude products of these isocyanates are used. 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- or 4,4'-diphenylmethane diisocyanate (MDI), poly Examples include methylene polyphenyl isocyanate (crude MDI), naphthylene-1,5-diisocyanate, and triphenylmethane-4,4 ′, 4 ″ -triisocyanate.
Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms such as isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and norbornane diisocyanate.
As the araliphatic isocyanate, an araliphatic diisocyanate having 8 to 12 carbon atoms is used, and examples thereof include xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.
Examples of the modified polyisocyanate include urethane-modified MDI or TDI (such as sucrose-modified TDI and castor oil-modified MDI) and carbodiimide-modified MDI.

Of the hollow microspheres (C), hollow microspheres made of a thermoplastic resin or a thermosetting resin are preferred, more preferably hollow microspheres made of a thermoplastic resin, particularly preferably polyacrylonitrile, polymethacrylonitrile, polyacrylic acid. Two or more copolymers selected from methyl, polymethyl methacrylate, polyvinyl chloride and polyvinylidene chloride, most preferably two selected from polyacrylonitrile, polymethacrylonitrile, polymethyl acrylate and polymethyl methacrylate The above copolymer.
Examples of the thermoplastic resin include polyvinylidene chloride, polymethyl methacrylate and polyacrylonitrile.
Examples of the thermosetting resin include phenol resin, epoxy resin, and urea resin.

The volume average particle diameter (μm) of the hollow microspheres (C) is preferably 0.5 to 100, more preferably 1 to 80, particularly preferably 5 to 70, and most preferably 10 to 60. Within this range, the handleability, smoothness and fineness after curing, etc. are further improved.
The true specific gravity of the hollow microsphere (C) is preferably 0.005 to 0.1, more preferably 0.009 to 0.09, particularly preferably 0.015 to 0.08, and most preferably 0.02 to 0.02. 0.07. When it is within this range, the handleability and the like are further improved.
Specific examples of such hollow microspheres (C) that can be obtained from the market include Expandel 551DE40d42, Expandel 551DE40d60, Expandel 551DE40d60, Expandel 461DE40d60, Expandel 461DE20d70, Expandel 092DE40d30 (Exp. Pancell Corporation), Matsumoto Microsphere F-80ED and MFL series (Matsumoto Yushi Seiyaku Co., Ltd.) and the like.

The dehydrating agent (D) is used to smoothen the surface after curing by preventing moisture from being mixed into the overlaying agent, or to improve the adhesion by preventing the foaming phenomenon that occurs at the joint between the overlaying agents. It is done.
Of the known dehydrating agents, neutral or alkaline dehydrating agents are preferred, more preferably calcium oxide, calcium sulfate (hemihydrate gypsum), calcium chloride and molecular sieves, particularly preferably calcium chloride and molecular sieves, most preferably molecular sieves. It is.
The volume average particle diameter (μm) of the dehydrating agent (D) is preferably 0.05 to 50, more preferably 0.07 to 40, particularly preferably 0.09 to 30, and most preferably 0.1 to 20. is there. Within this range, the surface area per unit weight is large and sufficient dehydrating ability is exhibited.
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, and most preferably 0.2 to 40. Within this range, water molecules can be adsorbed efficiently.

  In the placement agent of the present invention, other additives (E) may be used as long as the effect of the placement agent of the present invention is not impaired. (E) includes urethanization catalysts (amine catalysts such as triethylenediamine, N-ethylmorpholine, diethylethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7; stannous octylate, dibutyl Metal catalysts such as tin dilaurate and lead octylate), plasticizers (xylene oligomers, dioctyl phthalate, dioctyl adipate, etc.), thixotropic agents (particulate silica (particle size 100 nm or less), hydrogenated castor oil, organic bentonite Etc.), foam stabilizers (silicone foam stabilizers, etc.), inorganic fillers (calcium carbonate, talc, aluminum hydroxide, mica, milled fiber, etc.), organic fillers (such as pulverized thermosetting resin), ultraviolet rays Absorbers, anti-aging agents, antioxidants, colorants (dyes, pigments), flame retardants, antifungal agents, antibacterial agents, etc. It can be closed.

The contents of the polyol (A) and the organic polyisocyanate (B) are determined according to the isocyanate index [(number of NCO groups / number of active hydrogen atoms) × 100]. The isocyanate index is preferably 80 to 140, more preferably 85 to 130, particularly preferably 90 to 120, and most preferably 95 to 115. Within this range, the strength and toughness after curing are further improved.
The total content (% by weight) of (A) and (B) is 50 to 90 based on the total weight of (A), (B), (C), (D), (W) and (E). More preferably, it is 55-85, Most preferably, it is 60-80, Most preferably, it is 65-75. Within this range, the toughness after curing will be good.

The content (% by weight) of the hollow microsphere (C) is 0.01 to 40 based on the total weight of (A), (B), (C), (D), (W) and (E). Is more preferably 0.02 to 35, particularly preferably 0.03 to 30, and most preferably 0.05 to 25. If (C) having a specific gravity in the above range is used in a content in the above range, the density of the cured product will be in the range of 0.3 to 0.6, and an easily cut hardened product will be obtained.
In the present invention, the density of the cured product refers to a cured product obtained by leaving a resin placed at 300 mm × 300 mm × 50 mm or more at 25 ° C. for 1 hour, followed by heating and curing at 70 ° C. for 10 hours, and then allowing to cool for 8 hours. Cut out the test piece in the center section cut 10 mm or more with respect to the thickness and 50 mm or more with respect to the length and width direction, and the weight of the test piece is divided by the volume calculated from the product of the lengths of the three sides. The density of the cured product.

  The content (% by weight) of the dehydrating agent (D) is preferably 1 to 30, based on the total weight of (A), (B), (C), (D), (W) and (E), More preferably, it is 2-25, Most preferably, it is 3-20, Most preferably, it is 5-15. Within this range, the smoothness and adhesiveness of the surface after curing are further improved.

  The content (% by weight) of the organic lubricant (W) is 0.1 to 30 based on the total weight of (A), (B), (C), (D), (W) and (E). More preferably, it is 0.2-25, Most preferably, it is 0.5-20, Most preferably, it is 1-15. Within this range, the smoothness after curing becomes even better.

  The preferred amount of the other additive (E) used with respect to the total weight of the overlay of the present invention is 0.001 to 0.01% by weight for the urethanization catalyst, and 0.5 to 15 for the thixotropic agent. % By weight (especially 1 to 10% by weight), 1 to 40% by weight of plasticizer, 0.5 to 20% by weight of inorganic filler, 0.1 to 10% by weight of organic filler, Each is 0.1 to 5% by weight.

  The overlay of the present invention is in any form as long as it contains polyol (A), organic polyisocyanate (B), hollow microsphere (C), dehydrating agent (D) and organic lubricant (W). However, from the viewpoint of the reactivity between (A) and (B), 2 of 1 liquid (H component) composed of polyol (A) and 1 liquid (NCO component) composed of organic polyisocyanate (B). A two-part curable form composed of a liquid is preferable, and more preferably, one liquid consisting of a polyol (A), hollow microspheres (C), a dehydrating agent (D), and an organic lubricant (W) and an organic polyisocyanate (B ), A two-component curable type composed of two liquids of a hollow microsphere (C) and a single liquid consisting of a dehydrating agent (D), particularly preferably the weight ratio of the hollow microsphere (C) and the dehydrating agent (D) is , Each (content in H component): (content in NCO component) = 40 60 to 60: A two-part curable 1:40.

The overlaying agent of the present invention can be produced in the same manner as in a normal method, and various raw materials are mixed using a mixing vessel equipped with a propeller-type or vertical-type stirring blade, a planetary mixer, or a Hobart mixer. Manufactured by mixing. In particular, when the proportion of the hollow microspheres (C) is high, the stirring share becomes high, and therefore it is preferable to use a planetary mixer.
As an example of the embodiment for producing the overlaying agent of the present invention, the following process procedure may be mentioned for a production method using a planetary mixer.
(1) First, a liquid component (polyol (A), colorant, plasticizer, etc. for H component, organic polyisocyanate (B), colorant, plasticizer, etc. for NCO component) is mixed with a planetary mixer (for example, PLGM manufactured by Inoue Seisakusho Co., Ltd.). -400 type) is mixed and weighed into a mixing tank, and mixed for 10 minutes at low speed (revolution 14 rpm, rotation 44 rpm) and room temperature (10 to 35 ° C.).
(2) Subsequently, powder components are added in the order of hollow microspheres (C), organic lubricant (W), and other additives (E), and finally the dehydrating agent (D) is added. After charging, mix for 10 to 30 minutes at room temperature at low speed until the powder components are compatible with the liquid. After the powder component has become familiar with the liquid, it is mixed for 30 minutes at room temperature at high speed (21 rpm rotation, 66 rpm revolution) while degassing under reduced pressure to -0.9 MPa or less.
In order to further increase the smoothness after curing, it is preferable to deaerate under reduced pressure during mixing to remove bubbles contained in the overlay.
Further, the mixing temperature of the liquid component and the powder component may be raised below the melting point of the organic lubricant (W) (for example, if the melting point is 70 ° C., the temperature is raised to 50 ° C.). By increasing the temperature, pressure filling is facilitated.
(3) After completion of mixing, the blending tank is set in a ram press type filling machine (for example, PHL-400 type manufactured by Inoue Seisakusho Co., Ltd.), and a 20 L straight pail can is filled through a resin hose from the bottom valve while applying pressure.

The overlay of the present invention is suitable for producing a model material having a desired shape by mixing and discharging the H component and the NCO component using a two-liquid discharger. As an example of the embodiment of the method of using the overlaying agent of the present invention, the following process procedure can be given for the overlaying operation by the two-liquid discharger.
(1) The H component and the NCO component respectively filled in the pail can are set in a two-liquid discharge machine having two pump units that can suck and feed directly from the pail can.
The type of pump is preferably a plunger pump or a snake pump, more preferably a snake pump (for example, manufactured by Hyojin Equipment Co., Ltd. Pale can discharger 2NTL20).
(2) The respective pumping amounts are set at such a ratio that the isocyanate index of the H component and the NCO component is within the above range.
(3) A static mixer (for example, Static Mixer 11 / 2-N30-131-F, manufactured by Noritake Company Limited) is installed in the line to the discharge port, and two liquids are discharged. The mixed liquid mixed by the static mixer is applied onto a core material (for example, rigid polyurethane foam Soflan board 80 manufactured by Axon Co., Ltd.) having an approximate target shape in advance.
(4) After primary curing at room temperature (10 to 35 ° C.) for 1 hour, post curing at 50 to 70 ° C. for 8 to 12 hours to obtain a model material having a desired shape.
If the reaction rate is increased, the placement agent of the present invention is cured until it exhibits sufficient physical properties even when left at room temperature. However, if necessary, it can be heated and post-cured to exhibit stable physical properties. The post-curing conditions are preferably 40 to 100 ° C., more preferably 50 to 70 ° C., preferably 5 to 14 hours, and more preferably 8 to 12 hours.

  A model (industrial model) is obtained by cutting the obtained model material with an NC machine or the like. Further, since the cutting surface of the present model is finished smoothly, it can be painted after the surface is ground with sandpaper (for example, No. 240). This model can be used for, for example, a full-scale model of a railway vehicle, a full-scale model of an automobile, an interior model of an automobile, and a full-scale model of home appliances.

[Examples] The present invention will be described in more detail with reference to the following 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 (A)
(A11): Polyether polyol having a hydroxyl value of 400 mgKOH / g, in which PO is added to glycerin. Viscosity: 0.38 Pa · s.
(A21): Polyether polyol having a hydroxyl value of 450 mgKOH / g, in which PO is added to ethylenediamine and then EO is added to the terminal. EO to PO weight ratio; EO / PO = 47.5 / 52.5. Viscosity: 1.15 Pa · s.

Organic polyisocyanate (B1): Polymethylene polyphenyl isocyanate (BASF Inoac Polyurethane “Luprinate M-20S”). Viscosity: 0.20 Pa · s.
Hollow microsphere (C1): Thermoplastic resin hollow microsphere (“Expancel 551DE” manufactured by Expancel). True specific gravity: 0.042, volume average particle size: 40 μm.
Dehydrating agent (D1): Molecular sieve ("Molecular sieve 3A-B powder" manufactured by Union Showa). Volume average particle diameter: 1 to 10 μm, pore diameter: 30 nm or less

Auxiliary (E)
(E1): Plasticizer; mesitylene-based xylene oligomer (“NIKANOL Y-51” manufactured by Fudou). Viscosity: 0.05 Pa · s.
(E2): thixotropic agent; particulate silica (“AEROSIL 200” manufactured by Nippon Aerosil Co., Ltd.). Volume average particle size; 12 nm.
Organic lubricant (W)
Fatty acid amide (W1)
(W11): Erucic acid amide powder (“Neutron-S” manufactured by Nippon Seika Co., Ltd.). Melting point: 84 ° C
(W12): N-oleyl-palmitic acid amide powder (“PNT” manufactured by Nippon Seika Co., Ltd.). Melting point: 69 ° C
(W13): Fatty acid amide powder of polyalkylene polyamine. Melting point: 60 ° C
Fatty acid ester (W2)
(W21): Stearyl 2-hydroxystearate (“ITOHWAX E-230” manufactured by Ito Oil Co., Ltd.). Melting point: 70 ° C
(W22): 12-hydroxymethyl stearate (“ITOHWAX E-210” manufactured by Ito Oil Co., Ltd.). Melting point: 52 ° C
Petroleum wax (W3)
(W31): Paraffin wax (“LUVAX 1266” manufactured by Nippon Seiwa Co., Ltd.). Melting point: 69 ° C
(W′1): N-hydroxyethyl-12-hydroxystearic acid amide powder (“ITOHWAX J-420” manufactured by Ito Oil Co., Ltd.). Melting point: 105 ° C
(W′2): N, N′-ethylene-bis-oleylamide powder (“ITOHWAX J-500” manufactured by Ito Oil Co., Ltd.). Melting point: 114 ° C

<Test method>
Curing speed: Adjust liquid temperature and room temperature to 25 ° C, weigh H component and NCO component so that the total weight is 200g in 1L paper cup, and after stirring for 30 seconds, become 100mm x 100mm x 30mm Dispose and test specimen. The almost center part of the test piece was touched with a finger, and the time from the start of stirring until the surface disappeared was taken as the curing rate.
density: A test piece of 100 mm × 200 mm × 30 mm is cut out from the center of a cured product of 500 mm × 500 mm × 50 mm, and the weight of the test piece is calculated from the product of the lengths of three sides in a room temperature-controlled at 20 to 25 ° C. Divided by the volume thus obtained to obtain the density.
hardness: The cured product is cut perpendicularly to the mounting surface with a band saw, and the central portion in the thickness direction of the cut surface is manufactured by Kobunshi Keiki Co., Ltd. in a room whose temperature is adjusted to 20 to 25 ° C. according to ASTM D2240 (1977 version). It was measured using a “D-type hardness meter”.

Bending strength: The cured product is cut into 80 mm × 10 mm × 4 mm to obtain a test piece, and the temperature is adjusted to 20 to 25 ° C. using an “Instron universal testing machine” manufactured by Shimadzu Corporation according to JIS K6911 (1992 version). The bending strength was measured with
Cutting resistance: The cured product is cut into 80 mm × 30 mm × 10 mm to obtain a test piece, which is cut with an NC machine in a room temperature-controlled at 20 to 25 ° C. (cutting blade: carbide slow-away tip, single blade, 16 mmφ, rotation speed: 5000 rpm 4-component dynamometer (KISTLER “9272”), amplifier: KISTLER “charge amplifier”, the resistance force that the cutting blade receives from the blade feed direction when the feed rate is 3000 mm / min and the cutting depth is 3 mm 5011 ", recorder:" WR7700 "manufactured by Graphtec Corporation).
Average surface roughness: The cured product is cut into 80 mm x 30 mm x 10 mm to make a test piece, which is cut with an NC machine in a room temperature-controlled at 20 to 25 ° C (cutting blade: flat end mill, high-speed four blades, 20 mmφ, rotation speed: 3000 rpm, feed The average surface roughness of the surface having a speed of 4000 mm / min and a cutting depth of 0.2 mm was measured with a non-contact type three-dimensional shape measuring instrument ("LM-3D system" manufactured by Keyence Corporation).

Reference Examples 1-15, Examples 1-3
After mixing each raw material into a planetary mixer (PLGM-400 model manufactured by Inoue Seisakusho Co., Ltd.) at the blending amounts (parts by weight) shown in Tables 1 and 2, the mixture was made uniform by revolving at 14 rpm and rotating at 44 rpm for 10 minutes. , Degassing for 30 minutes with rotation of 21 rpm, revolution of 66 rpm, −0.9 MPa or less, The overlay was obtained as a two-component curable type of H component and NCO component. Each component obtained was filled in a 20 L pail can with 18 L.
Next, the H component and the NCO component are fed at a speed of 2 L / min in total with a snake pump (Hyojin Equipment Co., Ltd. Pail Can Discharger Model 2NTL20), and one Y-pipe feeding line is provided. Then, a static mixer (No. 1/1 / 2-N30-131-F type manufactured by Noritake Company Limited) and 30 elements were mixed and discharged. A rigid polyurethane foam of 500 mm × 500 mm × 50 mm was erected vertically, and the discharge liquid was placed on a surface of 500 mm × 500 mm with a thickness of 30 mm. After being left vertical at 25 ° C. for 1 hour, it was cured by heating at 70 ° C. for 10 hours. This was left to cool for 8 hours to obtain a cured product of the placement agent.
The evaluation results are shown in Tables 1 and 2.

Comparative Examples 1-9
Cured products were obtained in the same manner as in Reference Examples 1 to 15 and Examples 1 to 3 with parts by weight shown in Table 3.
The evaluation results are shown in Table 3.

Since the urethane-based overlay for a model material according to the present invention contains an organic lubricant having a melting point of 50 to 90 ° C., a placement resin with a smooth cutting surface can be obtained, and a finishing process at a low speed becomes unnecessary. Moreover, since it is lightweight, it can be suitably used, for example, when producing a design model of an actual size of an automobile.

Claims (8)

In the overlay for a model material consisting of polyol (A), organic polyisocyanate (B), hollow microsphere (C) and dehydrating agent (D), the melting point (JIS K0064-1992, 3.2 melting point test method) is 50 to 50. An overlay for a model material, comprising an organic lubricant (W) made of a polyamine fatty acid amide at 90 ° C.
The placement agent according to claim 1, wherein the content of the organic lubricant (W) is 0.1 to 30 parts by weight per 100 parts by weight of the placement agent. The polyol (A) comprises a polyhydric alcohol alkylene oxide adduct and / or a polyhydric phenol alkylene oxide adduct (A1) and an amine alkylene oxide adduct (A2), and the total weight of (A1) and (A2) The mounting agent according to claim 1 or 2, wherein (A1) is 60 to 99% by weight, (A2) is 1 to 40% by weight, and (A) has a hydroxyl number of 200 to 700 mgKOH / g. The placement agent according to any one of claims 1 to 3, wherein the content of the hollow microspheres (C) is 0.01 to 40% by weight based on the total weight of the placement agent. 1 liquid consisting of polyol (A), hollow microsphere (C), dehydrating agent (D) and organic lubricant (W), and consisting of organic polyisocyanate (B), hollow microsphere (C) and dehydrating agent (D) It is a 2 liquid hardening type comprised from 1 liquid, The dressing agent in any one of Claims 1-4. A method for producing a model material, comprising: a step of mixing and discharging the placement agent according to claim 5 by a two-liquid discharger to place it on a core material; and a step of curing the placement portion. A model material obtained by placing and curing the placement agent according to any one of claims 1 to 5 on a core material. A model formed by cutting the model material according to claim 7.