JP5084786B2 - Rigid polyurethane foam composition, rigid polyurethane foam, and synthetic wood using the same - Google Patents

Description

  The present invention relates to a rigid polyurethane foam composition, a rigid polyurethane foam, and a synthetic wood using the same.

  Conventionally, wood has been widely used for furniture and house decoration materials as is well known. However, in recent years, timber harvesting regulations such as southern ocean timber have been strengthened from the viewpoint of environmental protection, and there is a demand for non-timbering in the fields where timber has been used so far, and the development of timber substitutes Has been made.

  As such a wood substitute, Patent Document 1 discloses a panel member for a vehicle member made of a fiber reinforced resin (FRP) plate and a rigid polyurethane foam. However, since the panel material uses two different types of materials, two steps, that is, a manufacturing process of the FRP plate and a step of injecting and foaming the rigid polyurethane foam composition into the FRP plate are necessary, and productivity is increased. It was not enough. Moreover, when this rigid polyurethane foam is used alone, good cutting processability cannot be obtained.

Japanese Patent Laid-Open No. 11-042653

  This invention is made | formed in view of the said problem, and is providing the hard polyurethane foam composition which can manufacture the hard polyurethane foam excellent in design property, cutting workability, and screwing property in a short time. .

  The inventors of the present invention have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by using a specific polyol component in a specific ratio as the rigid polyurethane foam composition. The invention has been completed.

That is, the rigid polyurethane foam composition of the present invention is a rigid polyurethane foam composition comprising a polyol component (A) and an organic isocyanate component (B), wherein the polyol component (A) comprises sorbitol and sucrose. A polyether polyol (A1) obtained by addition polymerization of alkylene oxide with an average hydroxyl value of 400 to 800 mgKOH / g using at least one selected from the group consisting of 2 to 4 and an average hydroxyl value of 20 to 20 Polyether polyol (A2) which is 70 mg KOH / g, and 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pen Diol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane, and these as starting materials have an average hydroxyl value of 600 It contains a polyol (A3) which is at least one selected from the group consisting of polyether polyols obtained by addition polymerization of alkylene oxide so as to be ˜1800 mgKOH / g, and the blending ratio (weight ratio) is (A1) / ( A2) / (A3) =, wherein the 40 to 80/5 to 30/15 to 30.

  The rigid polyurethane foam of the present invention is obtained using the rigid polyurethane foam composition.

  The synthetic wood of the present invention is characterized by comprising the hard polyurethane foam.

  By using the hard polyurethane foam composition of the present invention, it is possible to obtain a hard polyurethane foam having excellent design properties, cutting processability, and screwability. Moreover, since synthetic wood can be manufactured only with a hard polyurethane foam, productivity can be improved.

Rigid polyurethane foam composition of the present invention, as the polyol component (A), such that at least one average hydroxyl value of the alkylene oxide as starting material selected from the group consisting of sorbitol and sucrose is 400~800mgKOH / g Addition-polymerized polyether polyol (A1), polyether polyol (A2) having 2 to 4 hydroxyl groups and an average hydroxyl value of 20 to 70 mgKOH / g, and 1,2-propanediol and 1,3-propanediol 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 1,8-octanediol, 1,9-nonanediol, diethylene Group consisting of recall, dipropylene glycol, 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane, and polyether polyol obtained by addition polymerization of alkylene oxide so as to have an average hydroxyl value of 600 to 1800 mgKOH / g. containing polyol (A3) is at least one selected from the blending ratio (weight ratio), is (A1) / (A2) / (A3) = 40~80 / 5~ 30 / 15~30 .

  The number of hydroxyl groups in the polyol of the present invention is the number of hydroxyl groups contained in one molecule, and in the polyol added with alkylene oxide, it means the number of hydroxyl groups contained in the starting material before addition of alkylene oxide.

  Moreover, the average hydroxyl value of the polyol of this invention is measured according to JISK1557.

  The polyether polyol (A1) used in the present invention has 4 to 8 hydroxyl groups and an average hydroxyl value of 400 to 800 mgKOH / g. Moreover, the preferable number of hydroxyl groups is 6-8, and a preferable average hydroxyl value is 400-600 mgKOH / g. By setting it within the above range, the design property, cutting workability, and screwing property of the obtained foam are improved.

  As such a polyether polyol, for example, a polyol having four hydroxyl groups such as pentaerythritol, a polyol having six hydroxyl groups such as sorbitol, and a polyol having eight hydroxyl groups such as sucrose are used as starting materials. Examples include those obtained by addition polymerization of alkylene oxides such as oxide and butylene oxide so that the average hydroxyl value is within the above range.

  The polyether polyol (A2) used in the present invention has 2 to 4 hydroxyl groups and an average hydroxyl value of 20 to 70 mgKOH / g. Moreover, a preferable average hydroxyl value is 30-60 mgKOH / g. By setting it within the above range, the design property, cutting workability, and screwing property of the obtained foam are improved.

  Examples of such polyether polyols include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexane Starting from polyols having two hydroxyl groups such as dimethanol, polyols having three hydroxyl groups such as glycerin and trimethylolpropane, and polyols having four hydroxyl groups such as pentaerythritol, the same alkylene as polyether polyol (A1) Oxide average water Those groups titer by addition polymerization such that the above-mentioned range and the like.

The polyol (A3) used in the present invention has 2 to 3 hydroxyl groups and an average hydroxyl value of 600 to 1800 mgKOH / g. By setting it within the above range, the design property, cutting workability, and screwing property of the obtained foam are improved. Examples of such polyols, for example, a polyol Le with polyol or three hydroxyl groups having two hydroxyl groups exemplified as the starting materials of the polyether polyol (A2) can be mentioned. Moreover, the thing which addition-polymerized the same alkylene oxide as polyether polyol (A1) so that an average hydroxyl value may be set to 600-1800 mgKOH / g is also mentioned by using these as starting materials.

  The blending ratio (weight ratio) of the polyether polyol (A1), polyether polyol (A2) and polyol (A3) of the present invention is (A1) / (A2) / (A3) = 30 to 90/5 to 35. / 5 to 35, preferably 40 to 80/5 to 30/15 to 30. By setting the blending ratio of each polyol within the above range, the resulting foam has good design properties, cutting processability, and screwability.

  Examples of the isocyanate compound used in the organic isocyanate component (B) used in the present invention include tolylene diisocyanate (TDI), diphenyl diisocyanate, polymethylene diisocyanate, diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, naphthalene diisocyanate, xylylene. Examples thereof include isocyanate compounds such as range isocyanate and triphenylmethane triisocyanate. Further, a urethane prepolymer modified product, a dimerized modified product, a trimerized modified product, a urea modified product, a carbodiimide modified product and the like modified with a polyhydric alcohol such as polyether polyol and trimethylolpropane may be used. Two or more of these isocyanate compounds may be used in combination. Among these, since the design property of the hard polyurethane resin to be obtained becomes better, TDI, MDI and those modified with polyether polyol are preferable.

  In the hard polyurethane foam composition of the present invention, those usually used for hard polyurethane foam compositions are used as the foaming agent. Examples of such foaming agents include water, hydrofluorocarbons such as HFC-134a, HFC-152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-365-mfc, methylene chloride, pentane, and cyclopentane. Low boiling point hydrocarbons, liquefied carbon dioxide, and the like. These may be used alone or in combination of two or more. Of these, water and liquefied carbon dioxide are preferably used because they are non-flammable and have a low global warming potential.

  Other polyols can be used for the polyol component (A) of the present invention to the extent that the effects of the present invention are not impaired. Examples of such polyols include polyester polyols and polycarbonate polyols.

  As for the blending ratio of the polyol component (A) and the organic isocyanate component (B) used in the present invention, the NCO / OH ratio (equivalent ratio of isocyanate group to active hydrogen group) is preferably 0.9 to 3.0, and preferably 9 to 1.5 is more preferable. By setting it within the above range, the resulting foam can have good cutting processability and screwability.

  In the rigid polyurethane foam composition of the present invention, a catalyst can be used to adjust reactivity and curing time. Examples of such a catalyst include tertiary amines, diazabicycloalkenes and salts thereof, and organometallic compounds that are usually used in rigid polyurethane foam compositions.

  Examples of the tertiary amine include triethylenediamine, triethylamine, tri-n-butylamine, N-methylmorpholine, dimethylethanolamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethyl. Hexamethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, 1,2-dimethylimidazole and the like can be mentioned.

  Examples of organometallic compounds include metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, and iron with organic acids such as octenoic acid and naphthenic acid, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyl. Examples thereof include metal chelate compounds such as tin diacetylacetonate, zirconium tetraacetylacetonate, titanium acetylacetonate, acetylacetone aluminum, acetylacetone cobalt, acetylacetone iron, acetylacetone copper, and acetylacetone zinc.

  Any of these catalysts can be used alone or in admixture of two or more.

  Moreover, a foam stabilizer can be used for the rigid polyurethane foam composition of this invention. As such a foam stabilizer, what is normally used for manufacture of a rigid polyurethane resin can be used, For example, silicone foaming agents, such as a polyalkylsiloxane-polyoxyalkylene block copolymer, are mentioned.

  Furthermore, the rigid polyurethane foam composition of the present invention is added with a filler, a surfactant, an antioxidant, a flame retardant, an antifungal agent, a deodorant, a dispersant, a discoloration inhibitor, a plasticizer, a fragrance and the like. Agents can be used.

  Although the manufacturing method of the rigid polyurethane foam of this invention is not specifically limited, The following method is mentioned as an example.

  First, as a polyol component (A), polyether polyol (A1), polyether polyol (A2), polyether polyol (A3) and a blowing agent, and if necessary, auxiliary agents such as a catalyst and a foam stabilizer are mixed in a predetermined amount. Subsequently, a predetermined amount of the polyol component (A) and the polyisocyanate component (B) are mixed using a stirrer such as a homodisper, or a low-pressure or high-pressure foaming machine, and the obtained mixed solution is poured into a sealed mold. After curing for a predetermined time and curing, the rigid polyurethane foam is obtained by demolding.

  The compressive strength of the rigid polyurethane foam of the present invention is preferably 1 to 20 MPa, and more preferably 2 to 15 MPa. By setting it within the above range, the resulting foam has good cutting workability.

  The flexural modulus of the rigid polyurethane foam of the present invention is preferably 1 to 15 MPa, and more preferably 2 to 10 MPa. By setting it within the above range, the resulting foam has good cutting workability.

  The rigid polyurethane foam of the present invention preferably has a ratio of compressive strength to flexural modulus (compressive strength / flexural modulus) of 1 to 2. By setting it within the above range, the resulting foam has good cutting workability.

  The hard polyurethane foam of the present invention can be further coated with a light-resistant paint or the like on the surface.

  The synthetic wood of the present invention uses a wood grain-shaped mold as a mold used when producing a rigid polyurethane foam, and has an appearance similar to that of wood.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited only to an Example. In the examples and comparative examples described later, “parts” and “%” represent parts by weight and weight%, respectively, unless otherwise specified.

<Raw materials>
(Polyether polyol A1-1)
Polyether polyol (polyether polyol A1-2) having an average hydroxyl value of 550 mgKOH / g obtained by addition polymerization of propylene oxide to sorbitol
Polyether polyol (polyether polyol A1-3) having an average hydroxyl value of 450 mgKOH / g obtained by addition polymerization of sucrose with propylene oxide
Polyether polyol (polyether polyol A2-1) having an average hydroxyl value of 480 mgKOH / g obtained by addition-polymerizing propylene oxide to glycerin
Polyether polyol (polyether polyol A2-2) having an average hydroxyl value of 56 mgKOH / g obtained by addition polymerization of propylene oxide to propylene glycol
Polyether polyol (polyether polyol A2-3) having an average hydroxyl value of 56 mgKOH / g obtained by addition polymerization of propylene oxide to glycerin
Polyether polyol having an average hydroxyl value of 39 mgKOH / g obtained by addition polymerization of propylene oxide and ethylene oxide to pentaerythritol (trade name: Hiflex 515, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(Polyol A3-1)
1,5-pentanediol (average hydroxyl value 1075 mgKOH / g)
(Polyol A3-2)
Polyether polyol (polyol A3-3) having an average hydroxyl value of 865 mgKOH / g obtained by addition polymerization of propylene oxide to trimethylolpropane
1,2-propanediol (average hydroxyl value 1471 mgKOH / g)
(Foaming agent)
Distilled water (catalyst)
33% by weight dipropylene glycol solution of triethylenediamine (trade name: TEDAL-33, manufactured by Tosoh Corporation)
(Isocyanate compound 1)
Polymethylene polyphenyl polyisocyanate containing 31% by weight of free isocyanate (isocyanate compound 2)
Polyol-modified polyisocyanate containing 29% by weight of free isocyanate (trade name: DK System B-2711, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

<Examples 1-8, Comparative Examples 1-3>
A polyol component (A) and an isocyanate component (B) having the composition shown in Table 1 were adjusted to a liquid temperature of 22 ° C. Subsequently, the polyol component (A) and the isocyanate component (B) were mixed, and then immediately stirred vigorously for 10 seconds at a rotation speed of 4500 rpm using a homodisper (manufactured by Toyo Seiki Co., Ltd.). This is put into a sealed metal mold (325 mm × 155 mm × 30 mm) shaped in a grain shape adjusted in advance to 55 ° C., cured at 55 ° C. for 10 minutes, and then demolded to obtain a rigid polyurethane foam. Obtained.

Evaluation of the obtained rigid polyurethane foam was performed by the following method. In addition, the measurement of each physical property used the hard polyurethane foam which left still for 24 hours at 25 degreeC after demolding a hard polyurethane foam.
<Designability>
The surface of the rigid polyurethane foam was observed, and the case where the grain of the mold appeared on the surface of the foam was marked with ◯, and the case where the grain did not appear was marked with x.
<Screwability>
Using a vibration drill and screwdriver (trade name: EZ6901, manufactured by Panasonic Electric Works Co., Ltd., screw tightening speed scale 5), a wood screw with a nominal diameter of 3.5 mm is turned into a rigid polyurethane foam until the vibration drill and screwdriver automatically stops. Typed in. The case where the difference between the screw top and the hard polyurethane foam surface was 1 mm or less was rated as “○”, and the case where the difference between the screw head top and the hard polyurethane foam surface exceeded 1 mm was marked as “X”.
<Cutability>
A hard polyurethane foam was cut using a panel saw for woodworking (trade name: KVPF-800FKLH1D1B, manufactured by Kyowa Kiko Co., Ltd.).
<Foam density>
It measured based on JISK7222.
<Bending elastic modulus>
In accordance with JIS A 9511, a test piece of 4 mm × 10 mm × 100 mm was cut out from the rigid polyurethane foam and measured with an Instron universal testing machine.
<Compressive strength>
In accordance with JIS A 9511, a 30 mm × 30 mm × 20 mm test piece was cut out from the rigid polyurethane foam, and the uniaxial compressive strength in the direction perpendicular to the foaming direction of the rigid polyurethane foam was measured with an Instron universal testing machine.

  As is clear from Table 1, in Examples 1 to 8, rigid polyurethane foams excellent in design, screwing and cutting workability are obtained.

  On the other hand, as in Comparative Example 1, when the blending amount of each polyol contained in the polyol component (A) is outside the scope of the present invention, the design property, screwing property and cutting workability are poor, and bending It can be seen that the elastic modulus and compressive strength are lowered.

  Moreover, when not using polyether polyol (A2) like the comparative example 2, it turns out that screwing property is bad and a bending elastic modulus and compressive strength become low.

  Furthermore, as in Comparative Example 3, when a polyether polyol having a hydroxyl number of 3 is used instead of the polyether polyol (A1), the screwing property and the cutting workability are poor.

  The hard polyurethane foam composition of the present invention can provide a hard polyurethane foam excellent in design, cutting processability, and screwability. Therefore, it can be used in fields where conventional synthetic wood is used, for example, furniture, house decoration materials, and the like.

Claims (3)

A hard polyurethane foam composition comprising a polyol component (A) and an organic isocyanate component (B), wherein the polyol component (A) is an alkylene oxide starting from at least one selected from the group consisting of sorbitol and sucrose the average hydroxyl value of the polyether polyol by addition polymerization such that the 400~800mgKOH / g (A1), polyether polyol an average hydroxyl value is the number of hydroxyl groups is 2 to 4 is 20~70mgKOH / g (A2), 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8 Octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane, and alkylene oxide so that the average hydroxyl value is 600 to 1800 mgKOH / g using these as starting materials The polyol (A3), which is at least one selected from the group consisting of polyether polyols obtained by addition polymerization, is included, and the blending ratio (weight ratio) is (A1) / (A2) / (A3) = 40 to 80 / 5 rigid polyurethane foam composition, which is a 30/15 to 30.
  A rigid polyurethane foam obtained from the rigid polyurethane foam composition according to claim 1.   A synthetic wood comprising the rigid polyurethane foam according to claim 2.