JP6754398B2 - Polyurethane resin composition - Google Patents

Description

The present invention relates to polyurethane resin compositions.

Conventionally, a polyurethane resin is produced by reacting a polyether polyol component containing a PO-EO block adduct of an active hydrogen-containing compound with an organic polyisocyanate component in the presence of carbon particles, a foaming agent, a catalyst, a foam stabilizer, and the like. (For example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2006-70118

However, when the polyurethane resin described in Patent Document 1 is made into a molded product, the product is deformed, voids (vacancy) are generated, and the filling (filling to the end of the mold is not completed). There is a problem that trouble) occurs.
An object of the present invention is to provide a polyurethane resin composition having good moldability such as moldability, voidness (no voids are generated), and filling property (filling up to the end of a mold).

As a result of diligent studies to solve the above problems, the present inventor has arrived at the invention shown below. That is, the present invention is a polyurethane resin composition obtained by reacting a raw material containing an active hydrogen component (A), a polyisocyanate component (B) and carbon particles (C), and is contained in the active hydrogen component (A). The following polyether polyol (A1) is 40 to 70 % by weight based on the weight of (A), and the following polyether polyol (A3) is 10 to 80% by weight based on the weight of (A) and aromatic diamine ( A). A polyurethane resin composition containing A2).
Polyether polyol (A1): A polyether polyol having a hydroxyl value of 10 to 60 (mgKOH / g) represented by the following general formula (1).
Polyether polyol (A3): A polyether polyol having a hydroxyl value of 10 to 60 (mgKOH / g) represented by the following general formula (2).

[In the general formula (1), X represents a residue obtained by removing all active hydrogen atoms from the g-valent active hydrogen-containing compound (a), and g represents an integer of 2 to 5. R ¹ O, R ² O and R ³ O each independently represent an alkyleneoxy group having 3 to 4 carbon atoms. a to f represent the average number of moles of alkyleneoxy group or ethyleneoxy group added, a and f each independently represent a number of 5 to 50, and c and d each independently represent a number of 0.5 to 50. , B and e each independently represent a number from 0 to 30, and {(R ² O) _c / (CH ₂ CH ₂ O) _d } represents a random addition. ]

The polyurethane resin composition of the present invention has good moldability such as moldability, void property, and fillability.

The polyurethane resin composition of the present invention is a polyurethane resin composition obtained by reacting a raw material containing an active hydrogen component (A), a polyisocyanate component (B) and carbon particles (C), and is a polyurethane resin composition obtained by reacting the active hydrogen component (A). ) Is a polyurethane resin composition containing 40 to 70 % by weight of the following polyether polyol (A1) based on the weight of (A). Polyether polyol (A1): A polyether polyol having a hydroxyl value of 10 to 60 (mgKOH / g) represented by the following general formula (1).

[In the general formula (1), X represents a residue obtained by removing all active hydrogen atoms from the g-valent active hydrogen-containing compound (a), and g represents an integer of 2 to 5. R ¹ O, R ² O and R ³ O each independently represent an alkyleneoxy group having 3 to 4 carbon atoms. a to f represent the average number of moles of alkyleneoxy group or ethyleneoxy group added, a and f each independently represent a number of 5 to 50, and c and d each independently represent a number of 0.5 to 50. , B and e each independently represent a number from 0 to 30, and {(R ² O) _c / (CH ₂ CH ₂ O) _d } represents a random addition. ]

Conventionally, a PO-EO block adduct of an active hydrogen-containing compound has been used as a polyether polyol component. However, in the present invention, the above general formula (1) {is used as a polyether polyol in the active hydrogen component (A). For example, when R ¹ , R ² and R ³ are propylene groups, a polyether having a structure of the active hydrogen-containing compound (a) in which PO and EO are randomly added between the PO block and the EO block, etc.} By containing 40 to 70 % by weight of the polyol (A1), it is possible to obtain a polyurethane resin composition having good moldability even if it contains carbon particles.

The g-valent active hydrogen-containing compound (a) in the polyether polyol (A1) when g represents an integer of 2 to 5 is a compound having 2 to 5 active hydrogens, and is a polyvalent alcohol (a1). , Polyvalent hydroxyl group-containing compound (a2) other than polyhydric alcohol, amino group-containing compound (a3), thiol group-containing compound (a4), phosphoric acid group-containing compound (a5), and compounds having two or more active hydrogen groups. At least one active hydrogen group-containing compound selected from the group consisting of (a6) is included.

Examples of the 2 to 5 valent polyhydric alcohol (a1) include divalent aliphatic alcohols having 2 to 20 carbon atoms (hereinafter, may be abbreviated as C), trihydric aliphatic alcohols having C3 to 20 and the like. Examples thereof include 4- to 5-valent aliphatic alcohols of C5 to 20.
Examples of the C2-20 divalent aliphatic alcohol include linear or branched aliphatic diols (ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol). Etc.) and alicyclic diols (cyclohexanediol, cyclohexanedimethanol, etc.) and the like.
Examples of the C3 to 20 trivalent aliphatic alcohol include aliphatic triols (glycerin, trimethylolpropane, etc.).
Examples of the 4- to 5-valent aliphatic alcohol of C5 to 20 include pentaerythritol, sorbitan, diglycerin and alkyl glucoside.
As the polyhydric alcohol (a1), from the viewpoint of moldability, a 2- to 5-valent aliphatic alcohol of C2 to 10 is preferable, and a 2- to 4-valent aliphatic alcohol of C2 to 10 is particularly preferable. Is a 2-3 valent aliphatic alcohol of C2-10, most preferably propylene glycol and glycerin.

Examples of the 2 to 5 valent multivalent hydroxyl group-containing compound (a2) other than the polyhydric alcohol (a1) include 2 to 5 valent polyhydric phenols. Specifically, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, anthracene, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene and the like. Examples include polyvalent phenol.

Examples of the 2 to 5 valent amino group-containing compound (a3) include amines and amino alcohols. Specifically, ammonia; monoamines such as C1-20 alkylamines (butylamine and the like) and aniline; linear or branched aliphatic polyamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; complex such as piperazine and N-aminoethylpiperazine. Cyclic polyamines; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; aromatic polyamines such as phenylenediamine, tolylenediamine and diphenylmethanediamine; alkanolamines such as triethanolamine; by condensation of dicarboxylic acids with excess polyamines. Examples of the obtained polyamide polyamine; polyether polyamine; hydrazine (hydrazine and monoalkyl hydrazine, etc.), dihydrazide (dihydrazide succinate, dihydrazide terephthalate, etc.), guanidine (butylguanidine, 1-cyanoguanidine, etc.) and the like can be mentioned.

The 2 to 5 valent thiol group-containing compound (a4) includes a polythiol compound. Examples of the polythiol include 2- to 5-valent multi-valent thiols. Specific examples thereof include ethanedithiol and 1,6-hexanedithiol.

Examples of the phosphoric acid compound (a5) include phosphoric acid, phosphorous acid and phosphonic acid.

The 2 to 5 valent compound (a6) having two or more kinds of active hydrogen groups has two or more kinds of active hydrogen groups (hydroxyl group, amino group, carboxyl group, thiol group, phosphate group, etc.) in the molecule. Examples of the compound include alkanolamine (monoethanolamine, diethanolamine, etc.), amino acid (aspartic acid, etc.), hydroxycarboxylic acid (citrate, etc.) and the like.

Examples of the 2 to 5 valent active hydrogen group-containing compound (a) include a polyhydric alcohol (a1), an amino group-containing compound (a3), and a compound (a6) having two or more active hydrogen groups from the viewpoint of moldability. At least one selected from the group consisting of is preferable, and polyhydric alcohol (a1) is more preferable.

In the general formula (1), g is an integer of 2 to 5, but from the viewpoint of moldability, an integer of 2 to 4 is preferable, and 2 or 3 is more preferable.
When g is 2 or more, the moldability is good, and when g is 5 or less, the moldability is good.

In the general formula (1), R ¹ , R ² and R ³ independently represent an alkylene group having 3 to 4 carbon atoms, and specifically, 1,2-propylene group, 1,3-propylene group, 1, Examples thereof include 2-butylene group, 1,3-butylene group and 1,4-butylene group.
Of these, 1,2-propylene groups and 1,3-propylene groups are preferable, and 1,2-propylene groups are more preferable, from the viewpoint of raw material viscosity (meaning handleability; the same applies hereinafter).

In the general formula (1), a and f each independently represent a number of 5 to 50, c and d each independently represent a number of 0.5 to 50, and b and e each independently represent a number of 0 to 30. Represents a number.
The a is 5 to 50, preferably 10 to 40, and more preferably 20 to 30 from the viewpoint of moldability.
From the viewpoint of moldability, b is 0 to 30, preferably 0 to 10, more preferably 0 to 5, and particularly preferably 0.
The c is 0.5 to 50, preferably 0.5 to 20, more preferably 0.5 to 10, particularly preferably 0.5 to 3, and most preferably 0.5 to 20 from the viewpoint of moldability. It is 2.
The d is 0.5 to 50 from the viewpoint of moldability, preferably 1 to 20, more preferably 2 to 10, and particularly preferably 2 to 6.
From the viewpoint of moldability, e is 0 to 30, preferably 0 to 10, more preferably 0 to 5, and particularly preferably 0.
The f is 5 to 50, preferably 5 to 20, and more preferably 5 to 10 from the viewpoint of moldability.

The hydroxyl value (mgKOH / g) of the polyether polyol (A1) is 10 to 60, but from the viewpoint of moldability, it is preferably 15 to 55, more preferably 18 to 50, particularly preferably 20 to 40, and most preferably. Is 25 to 30.
Examples of the method for measuring the hydroxyl value include the method described in JIS K1557-1.

As the polyether polyol (A1), specifically, PO and ethylene oxide (hereinafter abbreviated as EO) are added to glycerin with 0.3 to 300 mol of propylene oxide (hereinafter abbreviated as PO) added. In some cases), 0.3 to 300 mol of each was randomly added, and 0.3 to 300 mol of EO was added, and 0.2 to 200 mol of PO was added to propylene glycol, and PO and EO were added, respectively. Examples thereof include those in which 0.2 to 200 mol of EO is randomly added and 0.2 to 200 mol of EO is further added.
As (A1), one type may be used, or two or more types may be used in combination.

The content of the active hydrogen component (A) polyether polyol (A1) in the 4 0-7 0% by weight, from the viewpoint of moldability, good Mashiku is 45 to 65 wt%. When the content of the polyether polyol (A1) in (A) is 40 % by weight or more, the carbon particles (C) are uniformly dispersed in the polyurethane resin composition and are 70 % by weight or less. Therefore, the moldability becomes good.

Examples of the aromatic diamine (A2) essential as the active hydrogen component (A) of the present invention include aromatic amines having two or more amino groups.
Specific examples thereof include phenylenediamine, toluenediamine, diphenylmethanediamine, diethyltoluenediamine and t-butyltoluenediamine.
The content of the aromatic diamine (A2) is preferably 0.1 to 5.0% by weight, more preferably 0.1 to 1.0% by weight, based on the weight of (A).

From the viewpoint of moldability, the active hydrogen component (A) further contains a polyether polyol (A3) having a hydroxyl value of 10 to 60 (mgKOH / g) represented by the following general formula (2). , (A3) may be used alone or in combination of two or more. Polyether polyol (A3): A polyether polyol having a hydroxyl value of 10 to 60 (mgKOH / g) represented by the following general formula (2).

[In the general formula (2), Y represents the residue obtained by removing all active hydrogen atoms from the j-valent active hydrogen-containing compound (b), j represents an integer of 2 to 8, and R ⁴ O represents the number of carbon atoms. Represents 3 to 4 alkyleneoxy groups, h represents the average number of moles of alkyleneoxy groups added, i represents the average number of moles of ethyleneoxy groups added, and h and i each independently represent numbers 1 to 100. .. ]

The j-valent active hydrogen compound (b) in the above polyether polyol (A3) when j represents an integer of 2 to 8 is a compound having 2 to 8 active hydrogens, and is a polyhydric alcohol (b1). ), Polyhydric hydroxyl group-containing compound (b2) other than polyhydric alcohol, thiol group-containing compound (b3), phosphate group-containing compound (b4), and compound having two or more active hydrogen groups (b5). It contains at least one active hydrogen group-containing compound of choice.

Examples of the 2 to 8 valent polyhydric alcohol (b1) include C2 to 20 dihydric fatty alcohols, C3 to 20 trihydric fatty alcohols, and C5 to 20 4 to 5 valent aliphatic alcohols, 6 to 8 valent. Alcohol can be mentioned.
Of these, 2 to 20 dihydric fatty alcohols, C3 to 20 trihydric fatty alcohols, and C5 to 20 4 to 5 aliphatic alcohols are exemplified by 2 to 5 polyhydric alcohols in (A1). There is a polyhydric alcohol.
Examples of the hexahydric alcohol include saccharides (sucrose, glucose, mannose, fructose and derivatives thereof) and the like.
As the polyhydric alcohol (b1), a 4- to 8-valent aliphatic alcohol of C2 to 12 is preferable from the viewpoint of demoldability.

Examples of the multivalent hydroxyl group-containing compound (b2) other than the polyhydric alcohol (b1) include the polyhydric phenol exemplified in (a2) of (A1). Specifically, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, anthracene, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene and the like. Examples thereof include polyhydric phenol; polybutadiene polyol; and anthracene oil-based polyol.

The 2-8 valent thiol group-containing compound (b3) includes a polythiol compound. Examples of polythiols include 2- to 8-valent multivalent thiols. Specific examples thereof include ethanedithiol and 1,6-hexanedithiol exemplified in (a3) of (A1).

Examples of the phosphoric acid compound (b4) include phosphoric acid, phosphorous acid, and phosphonic acid exemplified in (a5) of (A1).

The 2-8 valent compound (b5) having two or more kinds of active hydrogen groups has two or more kinds of active hydrogen groups (hydroxyl group, amino group, carboxyl group, thiol group, phosphate group, etc.) in the molecule. Examples of the compound include alkanolamine (monoethanolamine, diethanolamine, etc.), amino acid (aspartic acid, etc.), hydroxycarboxylic acid (citrate, etc.) and the like.

As the active hydrogen group-containing compound (b), a polyhydric alcohol (b1) is preferable from the viewpoint of demoldability.

In the general formula (2), j is an integer of 2 to 8 from the viewpoint of moldability, and when j is 2 or more, the moldability is good, and when j is 8 or less, the moldability is good. It becomes.
Further, as (A3), it is preferable to use (A3) having 2 or 3 functional groups and (A3) having 8 functional groups in combination.

In the general formula (2), R ⁴ represents an alkylene group having 3 to ⁴ carbon atoms, specifically 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,3-. Examples thereof include a butylene group and a 1,4-butylene group. Of these, 1,2-propylene groups and 1,3-propylene groups are preferable, and 1,2-propylene groups are more preferable, from the viewpoint of raw material viscosity.

In the general formula (2), h represents the average number of moles of alkyleneoxy groups added, i represents the average number of moles of ethyleneoxy groups added, and h and i each independently represent numbers 1 to 100.
From the viewpoint of moldability, h is preferably 5 to 80, more preferably 10 to 50, particularly preferably 15 to 40, and most preferably 20 to 30.
From the viewpoint of demoldability, i is preferably 2 to 80, more preferably 3 to 50, particularly preferably 5 to 30, and most preferably 7 to 15.

The hydroxyl value of the polyether polyol (A3) (mgKOH / g) but is 10-6 0, from the viewpoint of moldability, the good Mashiku 18-50, particularly preferably 20-40, most preferably 25-30 Is.

From the viewpoint of demoldability, the content of the polyether polyol (A3) in the active hydrogen component (A) is preferably 10 to 80% by weight, more preferably 20 to 60% by weight, and particularly preferably 25 to 40% by weight. %.

The active hydrogen component (A) may further contain other active hydrogen compounds (A4) other than (A1) to (A3).
Examples of other active hydrogen compounds (A4) include the above-mentioned active hydrogen compounds (b), and polyether polyols and polyester polyols other than those of (A1) and (A3). As for (A4), one type may be used, or two or more types may be used in combination.
Of these, from the viewpoint of raw material viscosity, polyhydric alcohols (b1), amino group-containing compounds (b3) and polyalkylene glycols other than (A1) and (A3) are preferable, and polyhydric alcohols (b1) and It is an amino group-containing compound (b3).
Among the polyhydric alcohols (b1), from the viewpoint of the viscosity of the raw material, C2-10 2-trivalent aliphatic alcohols are preferable, and ethylene glycol, propylene glycol and glycerin are more preferable.
The content of the other polyol (A4) in the active hydrogen component (A) is preferably 0 to 30% by weight, more preferably 5 to 20% by weight, and particularly preferably 8 to 18% by weight from the viewpoint of raw material viscosity. Is.

As the polyisocyanate component (B), those conventionally used for polyurethane can be used.
Examples of such polyisocyanates include aromatic polyisocyanates (B1), linear or branched aliphatic polyisocyanates (B2), alicyclic polyisocyanates (B3), aromatic aliphatic polyisocyanates (B4), and modified products thereof. (B5) can be mentioned.
As (B), one type may be used, or two or more types may be used in combination.

Aromatic polyisocyanates (B1) include aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon in the NCO group; the same applies to the following polyisocyanates), aromatic triisocyanates having 6 to 20 carbon atoms, and these. Examples thereof include crude isocyanates of the above.
Specific examples include 1,3- and 1,4-phenylenediocyanates, 2,4- and 2,6-tolylene diisocyanates (hereinafter abbreviated as TDI), crude TDI, 2,4'-. And 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), polymethylene polyphenylene polyisocyanate (crude MDI), naphthylene-1,5-diisocyanate and triphenylmethane-4,4', 4'. '-Triisocyanate and the like can be mentioned.

Examples of the linear or branched aliphatic polyisocyanate (B2) include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples thereof include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate.

Examples of the alicyclic polyisocyanate (B3) include an alicyclic diisocyanate having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexanediisocyanate, norbornane diisocyanate and the like.

Examples of the aromatic aliphatic polyisocyanate (B4) include aromatic aliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate and α, α, α', α'-tetramethylxylylene diisocyanate.

The modified product (B5) includes the modified products (urethane group, carbodiimide group, allophanate group, urea group, burette group, isocyanurate group, oxazolidone group-containing modified product, etc.) of the above (B1) to (B4). Specific examples of the modified polyisocyanate include carbodiimide-modified MDI and urethane-modified MDI.

As the polyisocyanate component (B), modified products of aromatic polyisocyanates (B1) and (B1) are preferable from the viewpoint of moldability, and more preferably TDI, crude TDI, MDI and crude MDI, and modification of these isocyanates. It is at least one selected from the group consisting of substances, and particularly preferably at least one selected from the group consisting of MDI and crude MDI and modified products thereof.

The NCO content of the polyisocyanate component (B) is preferably 10 to 35% by weight, more preferably 15 to 35% by weight, and particularly preferably 20 to 30% by weight from the viewpoint of moldability.

The isocyanate index [(NCO group / active hydrogen atom-containing group) equivalent ratio × 100] when the active hydrogen component (A) and the polyisocyanate component (B) are reacted is preferably 70 to 70 from the viewpoint of moldability. It is 150, more preferably 80 to 130, particularly preferably 90 to 120, and most preferably 95 to 110.

The carbon particles (C) of the present invention preferably include carbon particles having a median diameter of 0.1 to 100 μm, and carbon particles dispersed in a polyether (polypropylene glycol or the like) may be used.
Examples of such carbon particles include carbon black (manufactured by Fuji Dye Co., Ltd., Fuji VL Black, etc.) and the like.
The amount of these carbon particles (C) used is preferably 0.1 to 15 parts by weight, more preferably 0.1 to 1 part by weight per 100 parts by weight of (A) from the viewpoint of dispersibility in the active hydrogen component (A). It is 5% by weight, particularly preferably 0.2 to 1% by weight.

When the active hydrogen component (A) and the polyisocyanate component (B) are reacted, the catalyst (D) and other additives (G) may be further contained in the raw material.
When the shape of the polyurethane resin composition is foam (foam), the foam stabilizer (E) and the foaming agent (F) may be contained.

As the catalyst (D), a known catalyst used as a urethanization catalyst can be used, and a tin compound (D1), a tertiary amine (D2) and the like can be used.
As the catalyst (D), one type may be used, or two or more types may be used in combination.

Examples of the tin compound (D1) include dibutyl stannic acid dilaurate and dibutyl stannic acid dioctylate. Further, as (D1), Neostan series {Neostan U-100 etc., manufactured by Nitto Kasei Co., Ltd.} and the like are commercially available.
Examples of the tertiary amine (D2) include triethylenediamine, N-ethylmorpholine, diethylethanolamine, N, N, N', N'-tetramethylhexamethylenediamine, 1-isobutyl-2-methylimidazole, 1, Examples thereof include 8-diazabicyclo- [5,4,0] -undecene-7 and bis (dimethylaminoethyl) ether (carboxylate), and a combination of two or more of these.
As (D2), triethylenediamine is preferable from the viewpoint of moldability and moldability.

As these catalysts (D), a combination of a tin compound (D1) and a tertiary amine (D2) is preferable from the viewpoint of moldability and moldability reactivity.

From the viewpoint of demoldability, the amount of (D1) used is preferably 0.001 to 5% by weight, more preferably 0.005 to 3% by weight, particularly based on 100 parts by weight of the active hydrogen component (A). It is preferably 0.008 to 2% by weight, most preferably 0.01 to 1% by weight.
The amount of (D2) used is preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight, based on 100 parts by weight of the active hydrogen component (A) from the viewpoint of moldability and moldability. %, Especially preferably 0.5 to 3% by weight, most preferably 1 to 2% by weight.
The weight ratio of (D1) to (D2) {(D1) / (D2)} is 0.01 / 99.99 to 99/1, more preferably 0.05, from the viewpoint of moldability and moldability. / 99.95 to 50/50, particularly preferably 0.1 / 99.9 to 20/80, and most preferably 1/99 to 3/97.
Further, as the catalyst (D), in addition to (D1) and (D2), a catalyst such as a titanium catalyst or a bismuth metal catalyst is preferably used in an amount of 50% by mass or less, more preferably 20% by mass, based on the weight of (D). It can also be used in combination below.

As the foam stabilizer (E), those generally used for producing polyurethane foam can be used, and dimethylsiloxane-based foam stabilizers [“SRX-253” and “PRX-607” manufactured by Toray Dow Corning Co., Ltd.) , Etc.] and polyether-modified dimethylsiloxane-based foam stabilizer ["SZ-1142", "SF-2904", "SRX-294A", "SH-193", "SZ-" manufactured by Toray Dow Corning Co., Ltd. 1720, "SZ-1675t", "SF-2936F", "SF-2904", "L-540", "L-3601" manufactured by Nippon Unicar Co., Ltd., and "B4900", "B8742LF2" manufactured by EVONIK. , "B8715LF2", etc.] and the like.

The amount of the foam stabilizer (E) used is preferably 0.05 to 5% by weight, more preferably 0.08 to 3% by weight, based on the weight of the active hydrogen component (A) from the viewpoint of impact resilience. is there. It is particularly preferably 0.1 to 2% by weight, and most preferably 0.15 to 1% by weight.

The foaming agent (F) includes water, liquefied carbon dioxide gas, and a low boiling point compound having a boiling point of −5 to 70 ° C.
Low boiling point compounds include hydrogen atom-containing halogenated hydrocarbons, low boiling point hydrocarbons and the like. Specific examples of hydrogen atom-containing halogenated hydrocarbons and low-boiling hydrocarbons include methylene chloride, HCFCs (hydrochlorofluorocarbons) (HCFC-123, HCFC-141b, HCFC-142b, etc.); HFCs (hydrofluorocarbons) (HFC- 152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc, etc.), butane, pentane, cyclopentane and the like.

Examples of the foaming agent (F) include water, liquefied carbon dioxide, methylene chloride, cyclopentane, HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, from the viewpoint of moldability. HFC-365 mfc and a mixture of two or more thereof are preferable, and water is more preferable.

The amount of the foaming agent (F) used is preferably 0.01 to 8% by weight, more preferably 0.02 to 5% by weight, based on the weight of the active hydrogen component (A) from the viewpoint of moldability and density. , Particularly preferably 0.05 to 1% by weight, most preferably 0.1 to 0.5% by weight.

Other additives (G) include colorants (dye and pigment), plasticizers (phthalates, adipates, etc.), organic fillers (synthetic short fibers, thermoplastic or thermosetting resins, etc.). Known auxiliary components such as spheres), flame retardants (phosphates and halogenated phosphates, etc.), antioxidants (triazole, benzophenone, etc.), antioxidants (hinderedphenol, hindered amine, etc.) can be mentioned.

The amount of these additives (G) added is preferably 1% by weight or less based on the weight of the active hydrogen component (A).
The plasticizer is preferably 10% by weight or less, more preferably 5% by weight or less.
The organic filler is preferably 50% by weight or less, more preferably 30% by weight or less.
The flame retardant is preferably 30% by weight or less, more preferably 2 to 20% by weight.
The antiaging agent is preferably 1% by weight or less, more preferably 0.01 to 0.5 parts by weight.
The antioxidant is preferably 1% by weight or less, more preferably 0.01 to 0.5% by weight.

The total density (g / cm ³ ) of the polyurethane resin composition of the present invention measured in accordance with JIS K6400 is preferably 0.5 to 1.2, more preferably 0.7 to 1, from the viewpoint of moldability. It is 0.1, and particularly preferably 0.8 to 1.05.

The polyurethane resin composition of the present invention can be produced by reacting a raw material containing the active hydrogen component (A), the polyisocyanate component (B), and carbon particles (C).
Specifically, from the group consisting of the active hydrogen component (A) and carbon particles (C), and if necessary, the catalyst (D), the foam stabilizer (E), the foaming agent (F) and other additives (G). It can be produced by mixing at least one selected kind to make a premix, and mixing the premix with the polyisocyanate component (B) and reacting them.
Further, the polyurethane resin composition of the present invention comprises the above-mentioned active hydrogen component (A), polyisocyanate component (B), carbon particles (C), catalyst (D), foam stabilizer (E) and foaming agent (F). A foam-like polyurethane resin composition (polyurethane foam) may be obtained by reacting a raw material containing the above.
Specifically, the active hydrogen component (A), carbon particles (C), catalyst (D), foam stabilizer (E), foaming agent (F) and, if necessary, other additives (G) are mixed and pre-mixed. A polyurethane foam can be produced by making a mix, mixing the premix with the polyisocyanate component (B), and reacting the mixture.

The polyurethane resin composition of the present invention has good moldability.
In particular, when the polyurethane resin composition of the present invention (particularly polyurethane foam) is made into a molded product by molding or the like, the active hydrogen component (A) and the polyisocyanate (B) are reacted (start of mixing raw materials containing these). When it is formed into a polyurethane resin composition, it can be integrally molded with other materials (for example, metal, glass, other inorganic substances, organic substances, etc.).
Therefore, it can be suitably used as a polyurethane resin composition for automobile interior materials and / or automobile exterior materials, and can be widely used particularly for shield materials for integrally molded windows and the like.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.
In addition, Examples 3 and 4 are reference examples.

<Examples 1 to 7 and Comparative Examples 1 to 7>
Active hydrogen component (A), carbon particles (C), catalyst (D), foam stabilizer (E) and foaming agent shown in Table 1 using a high-pressure foaming machine (mini-RIM machine manufactured by Polymer Engineering Co., Ltd.). The premix containing (F) and the polyisocyanate component (B) are mixed and injected into a 200 mm × 200 mm × 3 mm hermetically sealed mold and a glass integrally molded hermetically sealed test mold to obtain a foamy polyurethane resin composition. It was.

The foaming conditions are as follows.
<foaming conditions>
-Molding machine: MINI-RIM L-type head manufactured by Polymer Engineering Co., Ltd.-Discharge pressure: 17 to 19 MPa
・ Discharge rate: 150 g / sec ・ Liquid temperature: 40 to 50 ° C
・ Mold temperature: 105-125 ° C
・ Demolding time: 300 seconds

The following components were used as the components shown in Table 1.
Active hydrogen component (A)
Polyether polyol (A1-1): 1 mol of glycerin to which 71.7 mol of PO is added, 2.4 mol of PO and 16.5 mol of EO are randomly added, and 20.5 mol of EO is further added (hydroxyl value =). 28 mgKOH / g, EO unit content = 27% by weight, terminal EO unit content = 15% by weight, in general formula (1), X-[(PO) _23.9 -{(PO) _0.8 / (EO) _5.5 }-(EO) _6.8- H] Polyether polyol having a structure of ₃ )

Polyether polyol (A1-2): A product obtained by adding 47.0 mol of PO to 1 mol of propylene glycol, randomly adding 3.4 mol of PO and 4.5 mol of EO, and further adding 18.2 mol of EO (hydroxyl value). = 28 mgKOH / g, EO unit content = 30% by weight, terminal EO unit content = 20% by weight, in general formula (1), X-[(PO) _23.5 -{(PO) _1.7 / (EO) _2.3 }-(EO) _9.1- H] Polyether polyol having a structure of ₂ )

Polyether polyol (A1-3): To 1 mol of glycerin plus 71.7 mol of PO, 7.5 mol of EO was further added, 2.4 mol of PO and 9.0 mol of EO were randomly added, and further EO20.5. Mole added (hydroxyl value = 28 mgKOH / g, EO unit content = 27% by weight, terminal EO unit content = 15% by weight, in general formula (1), X-[(PO) _23.9- ( EO) _2.5 -{(PO) _0.8 / (EO) _3.0 }-(EO) _6.8- H] Polyether polyol having a structure of ₃ )

Polyether polyol (A1-4): To 1 mol of glycerin plus 64.5 mol of PO, 2.4 mol of PO and 11.5 mol of EO were randomly added, 7.5 mol of PO was added, and 20.5 mol of EO was further added. (Filament value = 28 mgKOH / g, EO unit content = 27% by weight, terminal EO unit content = 15% by weight, in general formula (1), X-[(PO) _21.4 -{(PO) _0.8 ) / (EO) _5.5 }-(PO) _2.5- (EO) _6.8- H] Polyether polyol having a structure of ₃ )

Polyether polyol (A1-5): To 1 mol of glycerin plus 64.5 mol of PO, 7.5 mol of EO was further added, 2.4 mol of PO and 9.0 mol of EO were randomly added, and 7.5 mol of PO. Addition of 20.5 mol of EO (hydroxyl value = 28 mgKOH / g, content of EO unit = 27% by weight, content of terminal EO unit = 15% by weight, in general formula (1), X-[ (PO) _21.4 − (EO) _2.5 − {(PO) _0.8 / (EO) _3.0 } − (PO) _2.5 − (EO) _6.8 −H] Polyether polyol having a structure of ₃ )

Polyether polyol (A1'-1): 1 mol of glycerin plus 69.3 mol of PO, 19.9 mol of EO and 2.4 mol of PO, and 20.5 mol of EO added (hydroxyl value = 28 mgKOH / g, and the content of EO units = 30 wt%, the content of terminal EO units = 15 wt%, in the general formula (1), X - _{[(PO) 23.1 - (EO)} 6.6 - (PO) 0.8 - (EO ) _6.8- H] Polyether polyol having a structure of ₃ )

Polyether polyol (A1'-2): 1 mol of glycerin plus 71.7 mol of PO, 16.5 mol of EO and 15.0 mol of PO, and 3.9 mol of EO added (hydroxyl value = 28 mgKOH / g, EO unit content = 15% by weight, terminal EO unit content = 3% by weight, in the general formula (1), X-[(PO) _23.9- (EO) _5.5- (PO) _5.0- (EO) ) _1.3- H] Polyether polyol having a structure of ₃ )

Polyether polyol (A1'-3): 1 mol of glycerin plus 71.7 mol of PO, 16.5 mol of EO and 2.4 mol of PO, and 20.5 mol of EO added (hydroxyl value = 28 mgKOH / g, and the content of EO units = 27 wt%, the content of terminal EO units = 15 wt%, in the general formula (1), X - _{[(PO) 23.9 - (EO)} 5.5 - (PO) 0.8 - (EO ) _6.8- H] Polyether polyol having a structure of ₃ )

Aromatic polyamine (A2-1): Toluenediamine Aliphatic polyamine (A2'-1): Ethylenediamine

Polyether polyol (A3-1): 1 mol of glycerin plus 81.2 mol of PO, with 27.3 mol of EO added (hydroxyl value = 28 mgKOH / g, EO unit content = 20 weight, general formula In (2), a polyether polyol having a structure of Y-[(PO) _27.1- (EO) _9.1- H] ₃ )

Polyether polyol (A3-2): 1 mol of glycerin added with PO73.9 and 36.9 mol of EO added (hydroxyl value = 28 mgKOH / g, EO unit content = 27% by weight, general formula ( In 2), a polyether polyol having a structure of Y-[(PO) _24.6- (EO) _12.3- H] ₃ )

Polyether polyol (A3-3): 1 mol of propylene glycol added with 46.7 mol of PO, and 27.3 mol of EO added (hydroxyl value = 28 mgKOH / g, EO unit content = 30% by weight, In the general formula (2), a polyether polyol having a structure of Y-[(PO) _23.4- (EO) _13.7- H] ₂ )

Polyether polyol (A3-4): 1 mol of sucrose with 214.8 mol of PO added and 72.7 mol of EO added (hydroxyl value = 28 mgKOH / g, EO unit content = 20% by weight, In the general formula (2), a polyether polyol having a structure of Y-[(PO) _26.9- (EO) _9.1- H] ₈ )

Aliphatic diol (A4)
(A4-1): Ethylene glycol

Isocinate component (B)
(B-1): Polymeric MDI (NCO content = 31%)

Carbon particles (C)
(C-1): Fuji VL Black 2000 (manufactured by Fuji Dye Co., Ltd.)

Catalyst (D)
(D-1): Neostan U-100 Organic Tin (manufactured by Nitto Kasei Co., Ltd.)
(D-2): Triethylenediamine / ethylene glycol = 33/67% by weight

Foam stabilizer (E)
(E-1): SF-8410 Foam regulator (manufactured by Toray Dow Corning Co., Ltd.)

Foaming agent (F)
(F-1): Water

The total densities of the polyurethane resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 7 were measured, and the moldability, void property and filling property were evaluated as moldability, and the determination was made according to the following criteria. .. The results are shown in Table 1.

<Physical property test>
Total density (kg / m ³ ): Measured according to JIS K6400.
<Demoldability>
It was confirmed whether or not the molded product was deformed when it was taken out from the closed mold.
○: Does not deform ×: Deforms <void property>
The presence or absence of voids (vacancy) inside or on the surface was visually observed by pushing the molded product by hand or letting it pass through the light.
◯: No voids ×: Voids <fillability>
The raw material was injected into a sealed mold of 200 mm × 600 mm × 3 mm, and the presence or absence of deficiency (trouble that the end of the mold could not be filled) of the demolded molded product was visually observed.
○: No lack of meat ×: There is lack of meat

As is clear from the results in Table 1, the urethane resin composition of the example using the polyether polyol (A1) and the aromatic polyamine (A2) satisfying the general formula (1) of the present invention has good moldability. I was able to get.
On the other hand, Comparative Example 1 in which the aromatic polyamine (B) is not used, Comparative Example 7 in which an aliphatic diamine is used instead of (B), and Comparative Example 4 in which d and e are 0 in the general formula (1) are demolded. Deformed by sex.
Comparative Example 2 which does not contain the polyether polyol (A1) essential for the present invention, Comparative Example 5 which does not contain a non-random portion (both c and d are 0) in the general formula (1), and (A1) / (A). ) Was less than 20% by weight. In Comparative Example 6, voids were generated. Further, in Comparative Example 3 in which C was 0 in the general formula (1), voids were generated, the product could not be filled to the end in the mold, and meat shortage occurred.

When the polyurethane resin composition of the present invention is made into a molded product by molding or the like, the active hydrogen component (A) and the polyisocyanate (B) are reacted (mixing of raw materials containing these is started) to obtain the polyurethane resin composition. When doing so, it can be integrally molded with other materials (for example, metal, glass, other inorganic substances, organic substances, etc.). Therefore, it can be suitably used as a polyurethane resin composition for automobile interior materials and / or automobile exterior materials, and can be widely used particularly for shield materials for integrally molded windows and the like.

Claims (3)

A polyurethane resin composition obtained by reacting a raw material containing an active hydrogen component (A), a polyisocyanate component (B), and carbon particles (C), wherein the following polyether polyol (A1) is contained in the active hydrogen component (A). ) Is 40 to 70 % by weight based on the weight of (A), and the following polyether polyol (A3) is a polyurethane containing 10 to 80% by weight based on the weight of (A) and aromatic diamine (A2). Resin composition.
Polyether polyol (A1): A polyether polyol having a hydroxyl value of 10 to 60 (mgKOH / g) represented by the following general formula (1).
Polyether polyol (A3): A polyether polyol having a hydroxyl value of 10 to 60 (mgKOH / g) represented by the following general formula (2).

[In the general formula (1), X represents a residue obtained by removing all active hydrogen atoms from the g-valent active hydrogen-containing compound (a), and g represents an integer of 2 to 5. R ¹ O, R ² O and R ³ O each independently represent an alkyleneoxy group having 3 to 4 carbon atoms. a to f represent the average number of moles of alkyleneoxy group or ethyleneoxy group added, a and f each independently represent a number of 5 to 50, and c and d each independently represent a number of 0.5 to 50. , B and e each independently represent a number from 0 to 30, and {(R ² O) _c / (CH ₂ CH ₂ O) _d } represents a random addition]

[In the general formula (2), Y represents a residue obtained by removing all active hydrogen atoms from the j-valent active hydrogen-containing compound (b), j represents an integer of 2 to 8, and R ⁴ has 3 carbon atoms. Represents alkylene groups of ~ 4, h represents the average number of moles of alkyleneoxy groups added, i represents the average number of moles of ethyleneoxy groups added, and h and i each independently represent numbers 1-100]. Claim that the polyisocyanate component (B) contains at least one selected from the group consisting of diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate and modified products thereof, and the NCO content of (B) is 10 to 35% by weight. The polyurethane resin composition according to 1 . The polyurethane resin composition according to claim 1 or 2 , further containing a catalyst (D) in the raw material, and the catalyst (D) containing a tin compound (D1) and / or a tertiary amine (D2).