JP2020164565A - Fiber reinforced plastic, fiber reinforced plastic article, and method for producing fiber reinforced plastic - Google Patents

Abstract

To provide a fiber reinforced plastic, a fiber reinforced plastic article and a method for producing fiber reinforced plastic, in which the work and cost can be reduced, and an improvement in the designability can be achieved.SOLUTION: A fiber reinforced plastic, which is a fiber reinforced plastic having a base material and a polyurethane resin impregnated in the base material, and in which the base material is a woven fabric containing reinforcing fibers, and the polyurethane resin is a reaction product of a polyisocyanate component containing an aliphatic polyisocyanate and/or a derivative thereof, and a polyol component having a hydroxyl value of 30 mgKOH/g or more and 1200 mgKOH/g or less.SELECTED DRAWING: None

Description

The present invention relates to fiber reinforced plastics, fiber reinforced plastic articles, and methods for producing fiber reinforced plastics.

Conventionally, a fiber reinforced plastic (FRP) including a fiber and a thermosetting resin impregnated in the fiber is known. Such fiber reinforced plastics are used in various industrial products, and the surface of the fiber reinforced plastics may be required to have a design depending on the application.

As a method for enhancing the design of the surface of the fiber reinforced plastic, for example, a method of preparing a mold having a satin-like uneven pattern on the surface and transferring the pattern on the surface to the fiber reinforced plastic has been proposed. (See, for example, Patent Document 1).

JP-A-9-109309

On the other hand, as described in Patent Document 1, in the method of transferring the pattern on the surface of the mold, it is necessary to prepare a dedicated mold having a fine structure, which is troublesome and costly. There is.

The present invention is a fiber reinforced plastic, a fiber reinforced plastic article, and a method for manufacturing a fiber reinforced plastic, which can reduce labor and cost and improve the design.

The present invention [1] comprises a base material and a polyurethane resin impregnated in the base material, the base material is a woven fabric containing reinforcing fibers, and the polyurethane resin is an aliphatic polyisocyanate and / or. It contains a fiber reinforced plastic which is a reaction product of a polyisocyanate component containing the derivative and a polyol component having a hydroxyl value of 30 mgKOH / g or more and 1200 mgKOH / g or less.

In the present invention [2], the polyisocyanate component contains a derivative of an aliphatic polyisocyanate, the derivative of the aliphatic polyisocyanate has an isocyanurate group and an allophanate group, and the content ratio of the allophanate group is isocyanate. The fiber-reinforced plastic according to the above [1], which is 10 mol or more and 90 mol or less with respect to 100 mol of a nurate group, is contained.

In the present invention [3], the polyol component contains a triol having a hydroxyl value of 100 mgKOH / g or more and 600 mgKOH / g or less and a diol having a hydroxyl value of 100 mgKOH / g or more and 300 mgKOH / g or less, and the triol is an oxy. A polyoxyalkylene triol having 2 to 3 carbon atoms in an alkylene group and / or a polyester triol which is a reaction product of a polybasic acid and / or an alkyl ester thereof and a polyhydric alcohol, and the diol is an oxy. A polyoxyalkylene diol having 2 to 3 carbon atoms in an alkylene group and / or a polyester diol which is a reaction product of a dibasic acid and / or an alkyl ester thereof and a dihydric alcohol, which is the above [1] or It contains the fiber-reinforced plastic according to [2].

The present invention [4] includes the fiber-reinforced plastic according to any one of the above [1] to [3], wherein the aliphatic polyisocyanate contains pentamethylene diisocyanate.

In the present invention [5], the content ratio of the triol is 60 equivalent% or more and 95 equivalent% or less, and the content ratio of the diol is 5 equivalent% or more and 40 equivalent% or less with respect to the total amount of the polyol component. , Contains the fiber reinforced plastic according to the above [3] or [4].

The present invention [6] includes the fiber-reinforced plastic according to any one of the above [1] to [5], wherein the reinforcing fiber is a carbon fiber.

The present invention [7] relates to any one of the above [1] to [6], wherein the ratio of the base material to the total volume of the fiber reinforced plastic is 30% by volume or more and 60% by volume or less. Contains the listed fiber reinforced plastics.

The present invention [8] includes a fiber reinforced plastic article characterized in that the fiber reinforced plastic according to any one of the above [1] to [7] is provided on the outermost surface.

In the present invention [9], a substrate made of a woven fabric containing reinforcing fibers is placed in a mold, and a polyisocyanate component containing an aliphatic polyisocyanate and / or a derivative thereof in the mold. A casting step of casting a polyurethane resin composition containing a polyol component having a hydroxyl value of 30 mgKOH / g or more and 1200 mgKOH / g or less, and a curing step of reacting and curing the polyurethane resin composition are provided. Includes a method for manufacturing fiber reinforced plastics.

In the present invention [10], the polyisocyanate component contains a derivative of an aliphatic polyisocyanate, the derivative of the aliphatic polyisocyanate has an isocyanurate group and an allophanate group, and the content ratio of the allophanate group is isocyanate. The method for producing a fiber-reinforced plastic according to the above [9], which is 10 mol or more and 90 mol or less with respect to 100 mol of a nurate group.

In the present invention [11], the polyol component contains a triol having a hydroxyl value of 100 mgKOH / g or more and 600 mgKOH / g or less and a diol having a hydroxyl value of 100 mgKOH / g or more and 300 mgKOH / g or less, and the triol contains oxy. A polyoxyalkylene triol having 2 to 3 carbon atoms in the alkylene group and / or a polyester triol which is a reaction product of a polybasic acid and / or an alkyl ester thereof and a polyhydric alcohol, and the diol is an oxy. A polyoxyalkylene diol having 2 to 3 carbon atoms in the alkylene group and / or a polyester diol which is a reaction product of a dibasic acid and / or an alkyl ester thereof and a dihydric alcohol. The method for producing a fiber-reinforced plastic according to [10] is included.

The present invention [12] is any one of the above [9] to [11], wherein the fiber reinforced plastic is produced by the RTM method, the HP-RTM method, the WCM method, and / or the RIM method. The method for producing a fiber reinforced plastic described in 1.

In the fiber-reinforced plastic of the present invention, a polyurethane resin which is a reaction product of a polyisocyanate component containing an aliphatic polyisocyanate and / or a derivative thereof and a polyol component having a hydroxyl value of 30 mgKOH / g or more and 1200 mgKOH / g or less is used. Used. Since such a polyurethane resin has excellent followability to a base material, when the base material is a woven fabric containing reinforcing fibers, the design (unevenness, etc.) derived from the woven fabric is fiber-reinforced regardless of the mold. Can be applied to plastic.

Therefore, the fiber-reinforced plastic, the fiber-reinforced plastic article, and the method for producing the fiber-reinforced plastic of the present invention can improve the design and further reduce the labor and cost.

FIG. 1 is a photograph of the fiber reinforced plastic of Example 1 taken with an optical microscope in a 3D photographing mode. FIG. 2 is a photograph of the fiber reinforced plastic of Comparative Example 1 taken with an optical microscope in a 3D photographing mode.

In the present invention, fiber reinforced plastic (FRP: Fiber Reinforced Plastics) refers to a plastic reinforced by putting a base material (reinforced fiber) in a polyurethane resin.

More specifically, the fiber reinforced plastic includes a base material containing fibers and a polyurethane resin impregnated in the base material, and preferably comprises a base material and a polyurethane resin.

In the fiber reinforced plastic, the base material is a woven fabric containing reinforcing fibers, preferably a woven fabric made of reinforcing fibers.

Examples of the reinforcing fibers include carbon fibers, glass fibers, aramid fibers, boron fibers, metal fibers, cellulose nanofibers, and artificial spider silk. The reinforcing fibers can be used alone or in combination of two or more.

Preferred examples of the reinforcing fiber include carbon fiber, glass fiber, and aramid fiber. In other words, the reinforcing fibers preferably consist of at least one selected from the group consisting of carbon fibers, glass fibers and aramid fibers.

As the reinforcing fiber, carbon fiber and glass fiber are more preferable, and carbon fiber is particularly preferable, from the viewpoint of thinning and weight reduction of the fiber reinforced plastic.

The carbon fiber is not particularly limited, and examples thereof include pitch-based carbon fiber, PAN (polyacrylonitrile) -based carbon fiber, and rayon-based carbon fiber. The carbon fibers can be used alone or in combination of two or more.

As the carbon fiber, PAN (polyacrylonitrile) -based carbon fiber is preferable.

Then, the woven fabric made of reinforcing fibers is formed by weaving the reinforcing fibers by a known method. The method for producing the woven fabric is not particularly limited, and examples thereof include plain weave, twill weave, satin weave, saaya weave, and checkered weave.

Examples of the woven fabric include plain woven fabric, twill woven fabric, red woven fabric, saaya woven fabric, checkered woven fabric, and uniaxial woven fabric and multi-axis woven fabric. As the woven fabric, these can be used alone or in combination of two or more. As the woven fabric made of reinforcing fibers, a plain woven fabric and a twill woven fabric are preferable, and a twill woven fabric is more preferable.

Further, in the woven fabric, the reinforcing fibers constituting the weft and the warp are preferably used as a fiber bundle.

The number of reinforcing fibers per bundle of fiber bundles (number of filaments: K (× 10 ³ fibers / bundle)) is not particularly limited, but the design (texture) of the reinforcing fibers is expressed on the surface of the fiber reinforced plastic. From the viewpoint, for example, 10 (0.01K) or more, preferably 100 (0.1K) or more, more preferably 1000 (1K) or more, still more preferably 3000 (3K) or more. For example, it is 100,000 (100K) or less, preferably 70,000 (70K) or less, more preferably 50,000 (50K) or less, and further preferably 24,000 (24K) or less.

The thickness of the weft and the warp is not particularly limited, but is, for example, 0.5 mm or more, preferably 1.0 mm or more, and for example, 30 mm or less, preferably 10 mm or less.

When the thickness of the weft and the warp is within the above range, the polyurethane resin can easily follow the woven fabric, and the design can be improved.

Further, the woven fabric made of reinforcing fibers can be used alone (one sheet), or can be used in a plurality of layers.

From the viewpoint of design, it is preferable to use a plurality of woven fabrics in layers.

When a plurality of woven fabrics are used, each woven fabric may have the same weave and the number of reinforcing fibers per bundle of fiber bundles, or may be different from each other.

When a plurality of woven fabrics are used, the number of woven fabrics is, for example, 2 or more, preferably 3 or more, and for example, 20 or less, preferably 10 or less.

The polyurethane resin can be obtained as a reaction product by reacting and curing a polyurethane resin composition containing a polyisocyanate component and a polyol component. That is, the polyurethane resin is a cured product of the polyurethane resin composition.

More specifically, the polyurethane resin composition contains a polyisocyanate component and a polyol component.

The polyisocyanate component contains an aliphatic polyisocyanate and / or a derivative thereof.

The aliphatic polyisocyanate is, for example, ethylene diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate). , Pentamethylene diisocyanate (1,5-pentane diisocyanate, PDI), Hexamethylene diisocyanate (1,6-hexane diisocyanate, HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6 − Diisocyanate Examples thereof include aliphatic diisocyanates (aliphatic aliphatic polyisocyanates) such as methylcapate and dodecamethylene diisocyanate.

The aliphatic polyisocyanate includes, in addition to the above-mentioned chain aliphatic polyisocyanate, an alicyclic polyisocyanate containing an alicyclic.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, and 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate; IPDI), 4,4'-, 2,4'-or 2,2'-dicyclohexylmethane diisocyanate or a mixture thereof (hydrogenated MDI), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, Examples thereof include 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (hydrogenated XDI), and alicyclic diisocyanates such as norbornan diisocyanate (NBDI).

These aliphatic polyisocyanates can be used alone or in combination of two or more.

As the aliphatic polyisocyanate, from the viewpoint of availability, a chain aliphatic polyisocyanate is preferable, and pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI) are more preferable, and the polyurethane resin. From the viewpoint of design and mechanical properties, pentamethylene diisocyanate (PDI) is more preferable.

More specifically, pentamethylene diisocyanate (PDI) has lower crystallinity than hexamethylene diisocyanate (HDI) due to the asymmetry due to the odd number of methylene chains, and can improve the crosslink density of the polyurethane resin. By using pentamethylene diisocyanate (PDI) as the aliphatic polyisocyanate, the design and mechanical strength of the polyurethane resin can be improved.

Examples of derivatives of the aliphatic polyisocyanate include the above-mentioned aliphatic polyisocyanate (monomer) multimer (for example, dimer and trimeric (for example, isocyanurate modified product, iminooxadiazidinedione). Modified products), pentamers, hexamers, etc.), allophanate derivatives (for example, allophanate derivatives produced by the reaction of aliphatic polyisocyanates with monovalent alcohols (described later) and / or divalent alcohols (described later). ), Biuret derivatives (for example, biuret derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanate with water or amines), urea derivatives (for example, the above-mentioned aliphatic polyisocyanate produced by the reaction of diamine). Urea derivatives, etc.), oxadiazine trione derivatives (for example, oxadiazine trione derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanate with carbon dioxide), carbodiimide derivatives (for example, decarbonation of the above-mentioned aliphatic polyisocyanate). Carbodiimide derivatives produced by condensation reactions, etc.), polyol derivatives (for example, polyol derivatives (alcohol adducts) produced by the reaction of the above-mentioned aliphatic polyisocyanates with trivalent or higher valent alcohols (described later), etc.), and further. , Iminooxadiazinedione derivative of aliphatic polyisocyanate, uretdione derivative of aliphatic polyisocyanate and the like.

These aliphatic polyisocyanate derivatives can be used alone or in combination of two or more.

These aliphatic polyisocyanates and / or derivatives thereof can be used alone or in combination of two or more.

As the aliphatic polyisocyanate and / or a derivative thereof, a derivative of the aliphatic polyisocyanate is preferable, and an isocyanurate derivative of the aliphatic polyisocyanate and an allophanate derivative of the aliphatic polyisocyanate are more preferable.

In addition, the derivative of the aliphatic polyisocyanate more preferably contains an isocyanurate group and an allophanate group.

That is, the derivative of the aliphatic polyisocyanate is preferably a mixture (derivative composition) of the derivative of the aliphatic polyisocyanate from the viewpoint of design and mechanical strength, and more specifically, mainly of the aliphatic polyisocyanate. An allophanate-modified isocyanurate derivative of an aliphatic polyisocyanate containing an isocyanurate derivative and an allophanate derivative of an aliphatic polyisocyanate, and in some cases, a reaction product of the isocyanurate derivative of the aliphatic polyisocyanate and an alcohol (described later). Contains.

Examples of the aliphatic polyisocyanate in the derivative of the aliphatic polyisocyanate include pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI) from the viewpoint of designability and mechanical strength.

In such an aliphatic polyisocyanate derivative, the content ratio (molar ratio) of the isocyanurate group and the allophanate group is adjusted within a predetermined range from the viewpoint of designability and mechanical strength.

Specifically, in the derivative of the aliphatic polyisocyanate, the content ratio of the allophanate group is, for example, 5 mol or more, preferably 10 mol or more, more preferably 12 mol or more, based on 100 mol of the isocyanurate group. More preferably, it is 20 mol or more, further preferably 30 mol or more, particularly preferably 40 mol or more, and for example, 95 mol or less, preferably 90 mol or less, more preferably 80 mol or less, still more preferably. , 70 mol or less, particularly preferably 60 mol or less.

When the content ratio of the allophanate group is less than the above lower limit, when a monohydric alcohol is used in the production of an aliphatic polyisocyanate derivative described later, the trifunctional isocyanurate group is excessive with respect to the bifunctional allophanate group. Therefore, the crosslink density may increase and the design of the polyurethane resin may decrease.

On the other hand, if the content ratio of the allophanate group exceeds the above upper limit, when a monohydric alcohol is used in the production of the aliphatic polyisocyanate derivative described later, the allophanate group becomes excessive with respect to the isocyanurate group, so that the crosslink density May decrease, the mechanical strength (hardness, etc.) of the polyurethane resin decreases, and the durability may also be inferior.

On the other hand, when the content ratio of the allophanate group is within the above range, the crosslink density can be adjusted appropriately, so that a polyurethane resin having excellent design and mechanical strength can be obtained.

Further, in the derivative of the aliphatic polyisocyanate, the content ratio of the allophanate group is, for example, 9 mol or more, preferably 11 mol or more, more preferably 17 mol, based on 100 mol of the total amount of isocyanurate group and allophanate group. The above is more preferably 23 mol or more, particularly preferably 29 mol or more, and for example, 47 mol or less, preferably 44 mol or less, more preferably 41 mol or less, still more preferably 38 mol or less. ..

In the derivative of the aliphatic polyisocyanate, the content ratio of the isocyanurate group is, for example, 53 mol or more, preferably 56 mol or more, more preferably 59 mol or more, based on 100 mol of the total amount of the isocyanurate group and the allophanate group. More preferably, it is 62 mol or more, for example, 91 mol or less, preferably 89 mol or less, more preferably 83 mol or less, still more preferably 77 mol or less, and particularly preferably 71 mol or less.

The content ratios of the isocyanurate group and the allophanate group are the allophanate group and the isocyanurate group obtained from the NMR chart of the aliphatic polyisocyanate derivative measured by the ¹³ C-NMR method in accordance with the examples described later. It can be calculated from the molar ratio of.

In order to produce such an aliphatic polyisocyanate derivative, for example, first, the above-mentioned aliphatic polyisocyanate and alcohol are subjected to a urethanization reaction, and then an isocyanurate-forming reaction is carried out in the presence of an isocyanurate-forming catalyst. Alternatively, for example, a method in which an aliphatic polyisocyanate is first isocyanurate and then an alcohol is added to cause a urethanization reaction can be mentioned.

Preferably, first, the above-mentioned aliphatic polyisocyanate and alcohol are subjected to a urethanization reaction, and then an isocyanurate-forming reaction is carried out in the presence of an isocyanurate-forming catalyst.

Examples of the alcohol include monohydric alcohol and divalent alcohol.

Examples of the monohydric alcohol include a linear monohydric alcohol and a branched monohydric alcohol.

Examples of the linear monohydric alcohol include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n. -Undecanol, n-dodecanol (lauryl alcohol), n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n -C (carbon number, the same applies hereinafter) 1 to 20 linear monohydric alcohols such as nonadecanol and eikosanol can be mentioned.

Examples of the branched monohydric alcohol include isopropanol, isobutanol (isobutyl alcohol), sec-butanol, tert-butanol, isopentanol, isohexanol, isoheptanol, isooctanol, and 2-ethylhexane-1-ol. , Isononanol, isodecanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, and other branched forms. Examples thereof include branched monohydric alcohols of C3 to 20 such as alkanol (C5 to 20).

Examples of the dihydric alcohol include ethylene glycol, 1,3-propanediol, 1,4-butanediol (1,4-butylene glycol), 1,5-pentanediol, 1,6-hexanediol, and 1,4. Linear dihydric alcohols such as −dihydroxy-2-butene, diethylene glycol, triethylene glycol, dipropylene glycol and other linear alkane (C7-20) diols, such as 1,2-propanediol, 1 , 3-Butandiol (1,3-butylene glycol), 1,2-Butanediol (1,2-butylene glycol), Neopentyl glycol, 3-Methyl-1,5-Pentanediol, 2,2,2- Branched dihydric alcohols such as trimethylpentanediol, 3,3-dimethylolheptan, 2,6-dimethyl-1-octene-3,8-diol and other branched alkane (C7-20) diols, eg , 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, dihydric alcohols of C2-20 such as hydride bisphenol A, bisphenol A Can be mentioned.

These alcohols can be used alone or in combination of two or more.

As the alcohol, from the viewpoint of lowering the viscosity of the derivative of the aliphatic polyisocyanate, a monohydric alcohol is preferable, a linear monohydric alcohol of C1 to 20 and a branched monohydric alcohol of C3 to 20 are preferable. More preferably, a linear monohydric alcohol of C1 to 4 and a branched monohydric alcohol of C3 to 4 are mentioned, and more preferably, a branched monohydric alcohol of C3 to 4 is mentioned. However, isobutyl alcohol is particularly preferable.

If the derivative of the aliphatic polyisocyanate has a low viscosity, the compatibility with the polyol component can be improved, and the design of the polyurethane resin can be improved.

The mixing ratio of the alcohol is, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, still more preferably 0.2 parts by mass or more, based on 100 parts by mass of the aliphatic polyisocyanate. , 0.5 parts by mass or less, for example, 4.0 parts by mass or less, preferably 2.5 parts by mass or less, more preferably 1.5 parts by mass or less.

When the blending ratio of the alcohol is within the above range, the content ratio of the isocyanurate group and the allophanate group in the derivative of the aliphatic polyisocyanate can be adjusted within the above range.

As the urethanization reaction conditions, for example, the reaction temperature is, for example, room temperature (for example, 25 ° C.) or higher, preferably 40 ° C. or higher in an inert gas atmosphere such as nitrogen gas and under normal pressure (atmospheric pressure). For example, it is 100 ° C. or lower, preferably 90 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 10 hours or less, preferably 6 hours or less, and more preferably 3 hours or less.

Further, in the above urethanization reaction, known urethanization catalysts (for example, amines (described later), organometallic compounds (described later), etc.) may be blended. The blending ratio of the urethanization catalyst is not particularly limited, and is appropriately set according to the purpose and application.

This makes it possible to obtain an aliphatic polyisocyanate partially urethane-modified (that is, an aliphatic polyisocyanate composition containing a urethane-modified aliphatic polyisocyanate and a (unreacted) aliphatic polyisocyanate). it can.

The partially urethane-modified aliphatic polyisocyanate is then subjected to an isocyanurate-forming reaction in the presence of an isocyanurate-forming catalyst.

Examples of the isocyanurate-forming catalyst include tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, trimethylbenzylammonium and tributylbenzylammonium, and organic weak salts thereof, for example, trimethylhydroxypropylammonium (also known as: trimethylhydroxypropylammonium). Hydrooxides of trialkylhydroxyalkylammoniums such as N- (2-hydroxypropyl) -N, N, N-trimethylammonium), trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxyethylammonium and organic weakened salts thereof (eg). , N- (2-Hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate, etc.), eg, metals of alkylcarboxylic acids such as acetic acid, caproic acid, octyl acid, myristic acid, naphthenic acid, etc. Salts (eg alkali metal salts, magnesium salts, tin salts, zinc salts, lead salts, etc.), eg, metal chelate compounds of β-diketones such as aluminum acetylacetone, lithium acetylacetone, etc., eg aluminum chloride, boron trifluoride. Friedel-Crafts catalysts such as, for example, various organic metal compounds such as titanium tetrabutyrate, tributylantimon oxide, for example, aminosilyl group-containing compounds such as hexamethylsilazane and the like.

These isocyanurate-forming catalysts can be used alone or in combination of two or more.

The isocyanurate-forming catalyst preferably includes an organic weakened acid salt of trialkylhydroxyalkylammonium, and more preferably N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate. Can be mentioned.

The blending ratio of the isocyanurate-forming catalyst (converted to 100% of the active ingredient) is, for example, 0.001 part by mass or more, preferably 0.003 part by mass or more, based on 100 parts by mass of the aliphatic polyisocyanate. For example, it is 0.1 part by mass or less, preferably 0.05 part by mass or less.

The reaction conditions for the isocyanurate-forming reaction include, for example, an atmosphere of an inert gas such as nitrogen gas, under normal pressure (atmospheric pressure), and a reaction temperature of, for example, 50 ° C. or higher, preferably 70 ° C. or higher, more preferably. It is 80 ° C. or higher, for example, 120 ° C. or lower, preferably 100 ° C. or lower. The reaction time is, for example, 5 minutes or more, preferably 10 minutes or more, more preferably 15 minutes or more, and for example, 120 minutes or less, preferably 60 minutes or less.

Then, in the above-mentioned isocyanurate-forming reaction, when a predetermined reaction rate (isocyanate-based conversion rate) is reached, for example, phosphoric acid, monochloroacetic acid, benzoyl chloride, dodecylbenzenesulfonic acid, and toluenesulfonic acid (o- or p). -Toluenesulfonic acid) and its derivatives (eg, methyl o- or p-toluenesulfonic acid), toluenesulfonamides (o- or p-toluenesulfonic acid) and other reaction terminators are added to the reaction solution to catalyze. Is deactivated to stop the isocyanurate-forming reaction. In this case, an adsorbent that adsorbs the catalyst, such as a chelate resin or an ion exchange resin, can be added to stop the isocyanurate-forming reaction.

The conversion rate of the isocyanate group when the isocyanurate-forming reaction is stopped is, for example, 1% by mass or more, preferably 5% by mass or more, and for example, 20% by mass or less, preferably 15% by mass or less.

The conversion rate of isocyanate groups can be measured based on, for example, high-speed GPC, NMR, isocyanate group concentration, refractive index, density, infrared spectrum, and the like.

This allows the aliphatic polyisocyanate to undergo an isocyanurate-forming reaction.

Further, in this isocyanurate-forming reaction, since a partially urethane-modified aliphatic polyisocyanate is isocyanurate-ized, an allophanate-modified isocyanurate derivative is also produced together with the above-mentioned isocyanurate derivative.

Further, in the above-mentioned isocyanurate-forming reaction, in order to adjust the isocyanurate-forming, for example, an organic phosphite ester as described in JP-A-61-129173 is blended as a co-catalyst. You can also.

Examples of the organic phosphorous acid ester include an organic phosphorous acid diester and an organic phosphorous acid triester, and more specifically, for example, triethylphosphite, tributylphosphite, tridecylphosphite, tris ( Monophosphite species such as tridecyl) phosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, diphenyl (tridecyl) phosphite, for example, di Examples thereof include di, tri or tetraphosphite derived from polyhydric alcohols such as stearyl, pentaerythrityl, diphosphite, tripentaerythritol, triphosphite, tetraphenyl, dipropylene glycol, and diphosphite.

These organic phosphite esters can be used alone or in combination of two or more.

Preferred examples of the organic phosphite ester include monophosphite, and more preferably tridecylic phosphite and tridecylic phosphite.

The blending ratio of the organic phosphite ester is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, and more preferably 0.10 part by mass or more with respect to 100 parts by mass of the aliphatic polyisocyanate. For example, it is 1.0 part by mass or less, preferably 0.50 part by mass or less.

Further, in the above-mentioned isocyanurate-forming reaction, if necessary, a hindered phenolic antioxidant, for example, 2,6-di (tert-butyl) -4-methylphenol (BHT), Irganox 1010, Irganox 1076, Reaction stabilizers such as Irganox 1135 and Irganox 245 (all manufactured by BASF Japan, trade name) can also be blended.

The mixing ratio of the reaction stabilizer is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, preferably 1.0 part by mass or less, based on 100 parts by mass of the aliphatic polyisocyanate. Is 0.10 parts by mass or less.

Further, the above-mentioned cocatalyst and reaction stabilizer can be added at the time of the above-mentioned urethanization reaction.

Further, in the above-mentioned isocyanurate-forming reaction, a known reaction solvent may be blended, if necessary.

Then, after completion of the reaction, unreacted aliphatic polyisocyanate (catalyst, reaction solvent and / or catalyst deactivation agent when blended, catalyst, reaction solvent and / or catalyst deactivation agent) is added from the obtained reaction mixture. Is also included), for example, by distillation such as thin film distillation (Smith distillation) or by a known method such as extraction, a derivative of the aliphatic polyisocyanate can be obtained.

Further, after removing the unreacted aliphatic polyisocyanate, the above-mentioned reaction terminator can be added as a stabilizer at an arbitrary addition ratio to the obtained aliphatic polyisocyanate derivative.

As a result, a derivative of an aliphatic polyisocyanate containing an isocyanurate group and an allophanate group is obtained.

According to such an aliphatic polyisocyanate derivative, the design property and the mechanical strength can be improved.

Further, as the derivative of the aliphatic polyisocyanate, for example, by preparing two or more kinds of derivatives of the aliphatic polyisocyanate having different formulations from each other, the ratio of the isocyanurate group and the allophanate group can be adjusted to the above range. It can also be adjusted.

More specifically, for example, an isocyanurate derivative of an aliphatic polyisocyanate and an allophanate derivative of an aliphatic polyisocyanate are individually prepared, and by mixing them, an isocyanurate group and an allophanate group are contained. A derivative (derivative composition) of an aliphatic polyisocyanate can be obtained.

The isocyanurate derivative of the aliphatic polyisocyanate is a derivative that contains an isocyanurate group and does not contain an allophanate group or contains a trace amount (described later).

An isocyanurate derivative of an aliphatic polyisocyanate containing no allophanate group causes, for example, an isocyanurate-forming reaction of an aliphatic polyisocyanate in the presence of an isocyanurate-forming catalyst in the above-mentioned isocyanurate-forming reaction without adding an alcohol. By doing so, it can be obtained. The reaction conditions in the isocyanurate-forming reaction are the same as described above.

However, the isocyanurate group is easily formed by going through a urethanization reaction. Therefore, the isocyanurate-forming reaction can be promoted by adding a small amount of alcohol. In such a case, an isocyanurate derivative of an aliphatic polyisocyanate containing a trace amount of an allophanate group can be obtained.

An isocyanurate derivative of an aliphatic polyisocyanate containing a trace amount of an allophanate group can be obtained, for example, by the above method (first, the above-mentioned aliphatic polyisocyanate and an alcohol are urethanized, and then isocyanurate in the presence of an isocyanurate-forming catalyst. In the method of causing a urethanization reaction), the amount of alcohol compounded is relatively small.

In such a case, the blending ratio of the alcohol is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, for example, 0.5 part by mass or less, based on 100 parts by mass of the aliphatic polyisocyanate. Preferably, it is 0.3 parts by mass or less.

This makes it possible to suppress the amount of allophanate groups produced by the reaction between the aliphatic polyisocyanate and the alcohol.

Then, the obtained reaction product is subjected to an isocyanurate-forming reaction in the presence of an isocyanurate-forming catalyst. The reaction conditions in the isocyanurate-forming reaction are the same as described above.

In the isocyanurate derivative of the aliphatic polyisocyanate, the content ratio of the allophanate group is, for example, less than 10 mol, preferably 8 mol or less, more preferably 7 mol or less, and more preferably 7 mol or less, based on 100 mol of the isocyanurate group. , Usually 0 mol or more.

The allophanate derivative of the aliphatic polyisocyanate is a derivative that contains an allophanate group and does not contain an isocyanurate group or contains a trace amount (described later).

An allophanate derivative of an aliphatic polyisocyanate can be obtained, for example, by reacting the above-mentioned aliphatic polyisocyanate with the above-mentioned monohydric alcohol, and then performing an allophanation reaction in the presence of an allophanization catalyst.

Examples of the monohydric alcohol include the same alcohol as the above-mentioned monohydric alcohol (monohydric alcohol in isocyanurate formation), which can be used alone or in combination of two or more. Examples of the monohydric alcohol preferably include linear monohydric alcohols of C1 to 20, branched monohydric alcohols of C3 to 20, and more preferably linear monohydric alcohols of C1 to 4. C3-4 branched monohydric alcohols are mentioned, more preferably C3-4 branched monohydric alcohols are mentioned, and isobutyl alcohols are particularly preferable.

When producing an allophanate derivative of an aliphatic polyisocyanate, the proportion of alcohol is, for example, more than 3 parts by mass, preferably 3.2 parts by mass or more, more preferably more than 100 parts by mass of the aliphatic polyisocyanate. Is 3.5 parts by mass or more, for example, 50 parts by mass or less, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

The reaction conditions in the reaction between the aliphatic polyisocyanate and the alcohol include, for example, an atmosphere of an inert gas such as nitrogen gas, and a reaction temperature of, for example, room temperature (for example, 25 ° C.) or higher under normal pressure (atmospheric pressure). It is preferably 40 ° C. or higher, for example, 100 ° C. or lower, preferably 90 ° C. or lower. The reaction time is, for example, 0.05 hours or more, preferably 0.2 hours or more, and for example, 10 hours or less, preferably 6 hours or less.

As a result, the aliphatic polyisocyanate and the alcohol are urethanized.

Further, in the urethanization reaction, a known urethanization catalyst (for example, amines (described later), organometallic compound (described later), etc.) may be blended, if necessary. The blending ratio of the urethanization catalyst is not particularly limited, and is appropriately set according to the purpose and application.

Then, in this method, an allophanation catalyst is added to the obtained reaction solution, and the reaction product of the aliphatic polyisocyanate and the alcohol is subjected to the allophanation reaction.

Examples of the allophanate catalyst include an organic carboxylic acid bismuth salt such as bismuth octylate, and an organic carboxylic acid lead salt such as lead octylate.

These allophanation catalysts can be used alone or in combination of two or more.

The allophanation catalyst is preferably a lead organic carboxylic acid salt, and more preferably lead octylate.

The addition ratio of the allophanation catalyst is, for example, 0.001 part by mass or more, preferably 0.002 part by mass or more, and more preferably 0.01 part by mass or more with respect to 100 parts by mass of the aliphatic polyisocyanate. For example, it is 0.3 parts by mass or less, preferably 0.05 parts by mass or less, and more preferably 0.03 parts by mass or less.

The reaction conditions for the allophanation reaction include, for example, an atmosphere of an inert gas such as nitrogen gas, under normal pressure (atmospheric pressure), and a reaction temperature of 0 ° C. or higher, preferably 20 ° C. or higher, for example, 160 ° C. or lower. , Preferably 120 ° C. or lower. The reaction time is, for example, 30 minutes or more, preferably 60 minutes or more, and for example, 1200 minutes or less, preferably 600 minutes or less.

Then, in the above allophanation reaction, when a predetermined reaction rate (isocyanate group conversion rate) is reached, a reaction terminator is added to the reaction solution to inactivate the catalyst and stop the allophanation reaction. In this case, an adsorbent that adsorbs the catalyst, such as a chelate resin or an ion exchange resin, can be added to stop the allophanation reaction. Examples of the reaction terminator for terminating the allophanation reaction include the same reaction terminators as those for terminating the isocyanurate-forming reaction.

The conversion rate of the isocyanate group when stopping the allophanation reaction is, for example, 1% by mass or more, preferably 5% by mass or more, and for example, 20% by mass or less, preferably 15% by mass or less.

The conversion rate of isocyanate groups can be measured based on, for example, high-speed GPC, NMR, isocyanate group concentration, refractive index, density, infrared spectrum, and the like.

This allows the aliphatic polyisocyanate to undergo an allophanate reaction.

Further, in the above reaction, for example, the above-mentioned organic phosphite ester can be blended as a co-catalyst in order to adjust urethanization and allophanation. The organic phosphite ester can be used alone or in combination of two or more. Examples of the organic phosphite ester include monophosphites, and more preferably tridecylic phosphite.

The addition ratio of the organic phosphite ester is, for example, 0.01 part by mass or more, preferably 0.02 part by mass or more, and more preferably 0.03 part by mass or more with respect to 100 parts by mass of the aliphatic polyisocyanate. For example, it is 0.2 parts by mass or less, preferably 0.15 parts by mass or less, and more preferably 0.1 parts by mass or less.

Further, the above-mentioned cocatalyst and reaction stabilizer can be added at the time of the above-mentioned urethanization reaction.

Further, in the above-mentioned isocyanurate-forming reaction, a known reaction solvent may be blended, if necessary.

Then, after completion of the reaction, unreacted aliphatic polyisocyanate (catalyst, reaction solvent and / or catalyst deactivating agent when blended, catalyst, reaction solvent and / or catalyst deactivating agent) is added from the obtained reaction mixture. (Including) is removed by a known method such as distillation such as thin film distillation (Smith distillation) or extraction to obtain an allophanate derivative of aliphatic polyisocyanate. Further, after removing the unreacted aliphatic polyisocyanate, the above-mentioned reaction terminator can be added to the obtained allophanate derivative of the aliphatic polyisocyanate at an arbitrary addition ratio as a stabilizer.

In the allophanate derivative of the aliphatic polyisocyanate, the content ratio of the isocyanurate group is, for example, less than 10 mol, preferably 8 mol or less, more preferably 7 mol or less, and more preferably 7 mol or less, based on 100 mol of the allophanate group. Usually, it is 0 mol or more.

Then, by mixing the above-mentioned isocyanurate derivative of the aliphatic polyisocyanate and the above-mentioned allophanate derivative of the aliphatic polyisocyanate by a known method, an isocyanurate group and an allophanate group are obtained as a mixture (composition) thereof. A derivative of an aliphatic polyisocyanate having the above can be obtained.

The mixing ratio of the isocyanurate derivative of the aliphatic polyisocyanate and the allophanate derivative of the aliphatic polyisocyanate is adjusted so that the ratio of the allophanate group and the isocyanurate group in the obtained mixture is within the above-mentioned predetermined range.

Specifically, the isocyanurate derivative of the aliphatic polyisocyanate is preferably 50 parts by mass or more, for example, with respect to 100 parts by mass of the total amount of the isocyanurate derivative of the aliphatic polyisocyanate and the allophanate derivative of the aliphatic polyisocyanate. Is 60 parts by mass or more, more preferably 80 parts by mass or more, and for example, 96 parts by mass or less, preferably 90 parts by mass or less. The allophanate derivative of the aliphatic polyisocyanate is, for example, 4 parts by mass or more, preferably 10 parts by mass or more, for example, 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 20 parts by mass. It is as follows.

In the aliphatic polyisocyanate derivative (derivative composition), the unreacted aliphatic polyisocyanate monomer is, for example, 1.0 part by mass or less, preferably 1.0 part by mass or less, based on 100 parts by mass of the aliphatic polyisocyanate derivative. It is also permissible to contain it in an amount of 0.5 parts by mass or less.

Further, as the polyisocyanate component, an isocyanurate derivative and an allophanate derivative of an aliphatic polyisocyanate and other derivatives (a derivative excluding the isocyanurate derivative and an allophanate derivative of an aliphatic polyisocyanate) can also be used in combination.

Examples of other derivatives include derivatives other than the isocyanurate derivatives and allophanate derivatives of the aliphatic polyisocyanates among the above-mentioned derivatives of the aliphatic polyisocyanates, and are, for example, biuret derivatives, urea derivatives, oxadiazine trione derivatives, and carbodiimide derivatives. , Polyol derivatives, iminooxadiazinedione derivatives, uretdione derivatives and the like.

These other derivatives can be used alone or in combination of two or more.

The form in which the other derivative is contained is not particularly limited, and for example, the other derivative is produced as a by-product in each of the above reactions (urethanization reaction, isocyanurate-forming reaction, allophanate-forming reaction, etc.), and other The derivative may be contained in the aliphatic polyisocyanate derivative. Further, for example, another derivative prepared separately may be added to the polyisocyanate derivative.

The content ratio of the other derivative is preferably adjusted so that the ratio of the allophanate group and the isocyanurate group in the aliphatic polyisocyanate derivative (derivative composition) is within the above range.

More specifically, the other derivatives are, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 50 parts by mass or less, based on 100 parts by mass of the total amount of the aliphatic polyisocyanate derivative. It is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less.

Further, the polyisocyanate component may contain an aliphatic polyisocyanate and / or a derivative thereof alone, and may further contain another polyisocyanate and / or a derivative thereof.

Examples of other polyisocyanates and / or derivatives thereof include other polyisocyanate monomers (excluding aliphatic polyisocyanates here) and other polyisocyanate derivatives (here, derivatives of aliphatic polyisocyanates are excluded). ).

Examples of other polyisocyanate monomers include polyisocyanates such as aromatic polyisocyanates and aromatic aliphatic polyisocyanates.

Examples of the aromatic polyisocyanate include m- or p-phenylenediocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof (TDI), 4,4'-, 2,4'-. Alternatively, 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenedi isocyanate (NDI). ) And other aromatic diisocyanates.

Examples of the aromatic aliphatic polyisocyanate include 1,3- or 1,4-xylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylene diisocyanate or a mixture thereof (TMXDI), and the like. Examples thereof include aromatic aliphatic diisocyanates such as ω, ω'-diisocyanate-1,4-diethylbenzene.

These other polyisocyanate monomers can be used alone or in combination of two or more.

Examples of other polyisocyanate derivatives include multimers of the other polyisocyanate monomers described above (for example, dimer, trimeric, pentameric, and heptameric), and allophanate derivatives (eg, the above). Allophanate derivatives produced by the reaction of other polyisocyanate monomers with monovalent alcohol and / or dihydric alcohol), biuret derivatives (for example, other polyisocyanate monomers described above, water and amines). Biuret derivatives produced by reaction with other species, etc.), urea derivatives (for example, urea derivatives produced by reaction with other polyisocyanate monomers described above and diamine), oxadiazine trione derivatives (eg, described above). Oxadiazine trione derivatives produced by the reaction of other polyisocyanate monomers with carbon dioxide gas, etc.), carbodiimide derivatives (carbodiimide derivatives produced by the decarbonate condensation reaction of the other polyisocyanate monomers described above, etc.). ), Polyisocyanate derivatives (for example, polyol derivatives (alcohol adducts) produced by the reaction of the above-mentioned other polyisocyanate monomers with trivalent or higher valent alcohols), the above-mentioned other polyisocyanate monomers and low molecular weight described later. Examples thereof include a polyol and / or a polyol derivative (polyisocyanate group-terminated prepolymer) produced by reaction with a high molecular weight polyol described later (preferably a high molecular weight polyol described later).

These other polyisocyanate derivatives can be used alone or in combination of two or more.

These other polyisocyanates and / or derivatives thereof can be used alone or in combination of two or more.

In the polyisocyanate component, the content ratio of the component excluding the aliphatic polyisocyanate and / or its derivative (other polyisocyanate and / or its derivative) is, for example, relative to the total amount of the aliphatic polyisocyanate and / or its derivative. It is less than 50% by mass, preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 0% by mass.

That is, the polyisocyanate component preferably contains an aliphatic polyisocyanate and / or a derivative thereof alone, and more preferably contains a derivative of an aliphatic polyisocyanate alone.

The isocyanate group equivalent of the polyisocyanate component thus prepared is, for example, 150 or more, preferably 200 or more, and for example, 750 or less, preferably 500 or less.

The isocyanate group equivalent is synonymous with the amine equivalent, and can be determined by the method A or method B of JIS K 1603-1 (2007) (the same applies hereinafter).

The average number of functional groups of the polyisocyanate component is, for example, 2.00 or more, preferably 2.10 or more, and for example, 3.00 or less, preferably 2.90 or less, more preferably 2. It is .80 or less.

The isocyanate group content of the polyisocyanate component is, for example, 18% by mass or more, preferably 20% by mass or more, and for example, 30% by mass or less, preferably 28% by mass or less.

The isocyanate group content can be determined by the n-dibutylamine method based on JIS K 1556 (2006) (the same applies hereinafter).

The polyol component contains, for example, a polyol compound. The polyol compound is, for example, a compound having two or more hydroxyl groups in one molecule.

Examples of the polyol compound include a polyol having two hydroxyl groups in one molecule (hereinafter, diol), a polyol having three hydroxyl groups in one molecule (hereinafter, triol), and a polyol having four or more hydroxyl groups in one molecule. And so on. These polyol compounds can be used alone or in combination of two or more.

In these polyol compounds, each parameter (number of hydroxyl groups, hydroxyl value, etc.) and content ratio are appropriately adjusted so that the hydroxyl value of the entire polyol component is in the range described later.

Preferred examples of the polyol compound include diol and triol, and more preferably a combination of diol and triol. In other words, the polyol component preferably contains diol and triol.

Examples of the diol include a polyether diol, a polyester diol, a polycarbonate diol, a polyurethane diol, and the like. These diols can be used alone or in combination of two or more.

Preferred examples of the diol include a polyether diol and a polyester diol.

Examples of the polyether diol include a polyoxyalkylene diol having an oxyalkylene group having 2 to 3 carbon atoms and a polyoxyalkylene diol having an oxyalkylene group having 4 or more carbon atoms (polytetramethylene ether glycol, etc.). Can be mentioned. These polyether diols can be used alone or in combination of two or more.

As the polyether diol, preferably, a polyoxyalkylene diol having 2 to 3 carbon atoms in the oxyalkylene group can be mentioned.

Examples of the polyoxyalkylene diol having 2 to 3 carbon atoms in the oxyalkylene group include addition polymers of alkylene oxides having 2 to 3 carbon atoms (two or more kinds) using a low molecular weight diol, a low molecular weight diamine or the like as an initiator. (Including random and / or block copolymers of alkylene oxides).

The low molecular weight diol is a bifunctional low molecular weight polyol having two hydroxyl groups having a number average molecular weight of less than 300 (preferably less than 400), usually 40 or more, and is, for example, an aliphatic diol or an alicyclic diol. Aromatic diols and the like can be mentioned.

Examples of the aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, and 2 -Methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2,4-trimethylpentane- 1,3-diol, 1,6-hexanediol, neopentyl glycol, 1,5-heptanediol, 1,7-heptanediol, 3,3'-dimethylolheptan, 1,8-octanediol, 1,9 Examples thereof include −nonandiol, 1,10-decanediol, 1,11-undecanediol, 1,12-undecanediol, and 12-hydroxystearyl alcohol.

Examples of the alicyclic diol include hydrogenated bisphenol A, hydrogenated xylylene diol, cyclohexanediol, cyclohexanedimethanol, hydrogenated dimerdiol and the like.

Examples of the aromatic diol include bisphenol A, bishydroxyethyl terephthalate, catechol, resorcin, hydroquinone, 1,3- or 1,4-xylylene diol and the like.

These low molecular weight diols can be used alone or in combination of two or more.

A low molecular weight diamine is a compound having two amino groups having a number average molecular weight of less than 300 (preferably less than 400), usually 40 or more, and is, for example, ethylenediamine, 1,3-propanediamine, 1,3-. Or 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine , 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane, hydrazine, o, m or p-tolylene diamine (TDA, OTD) and the like.

These low molecular weight diamines can be used alone or in combination of two or more.

Preferred examples of the initiator include low molecular weight diols, and more preferably aromatic diols.

Examples of the alkylene oxide having 2 to 3 carbon atoms include ethylene oxide (also known as oxylane), trimethylene oxide (also known as oxetane), and propylene oxide (also known as methyloxylan).

These alkylene oxides can be used alone or in combination of two or more.

Examples of the alkylene oxide are preferably ethylene oxide and propylene oxide, and more preferably propylene oxide.

Specific examples of such polyoxyalkylene diols include polyoxyethylene glycol, polyoxypropylene glycol, and propylene oxide-ethylene oxide copolymer diols (random and / or block copolymers).

These polyoxyalkylene diols can be used alone or in combination of two or more.

The polyoxyalkylene diol is preferably polyoxypropylene glycol.

The hydroxyl value of the polyoxyalkylene diol is, for example, 65 mgKOH / g or more, preferably 100 mgKOH / g or more, more preferably 105 mgKOH / g or more, still more preferably 150 mgKOH / g or more, for example, 500 mgKOH / g or less. It is preferably 300 mgKOH / g or less, more preferably 290 mgKOH / g or less, and even more preferably 250 mgKOH / g or less.

When the hydroxyl value of the polyoxyalkylene diol is within the above range, the design and mechanical strength of the polyurethane resin can be improved.

The hydroxyl value is measured in accordance with the description of JIS K-1557-1 (2007) (the same shall apply hereinafter).

The number average molecular weight of the polyoxyalkylene diol is, for example, 300 or more, preferably 400 or more, more preferably 500 or more, and for example, 1200 or less, preferably 1000 or less.

The number average molecular weight is calculated by the following formula (the same applies hereinafter).

Number average molecular weight = 56100 × average number of functional groups / hydroxyl value The CPR (controlled polymerization rate) of the polyoxyalkylene diol is, for example, 5 or less, preferably 3 or less, more preferably 2 or less, still more preferably 1. It is, for example, 0 or more, preferably 0.01 or more, and more preferably 0.1 or more.

CPR is measured based on the method described in JIS K 1557-4 (2007) (the same applies hereinafter).

Examples of the polyester diol include a polyester diol which is a reaction product of a dibasic acid and / or an alkyl ester thereof and a dihydric alcohol.

Examples of the dibasic acid include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Azelaic acid, sebacic acid, hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, het acid and other aliphatic dibasic acids, orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, dimer acid Examples thereof include aromatic dibasic acids such as, and acid anhydrides thereof, and acid halides thereof. Examples of the acid anhydride include oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl anhydride (12 to 18 carbon atoms) succinic anhydride, tetrahydrophthalic anhydride and the like. Examples of the acid halide include oxalic acid dichloride, adipic acid dichloride, sebacic acid dichloride and the like.

These dibasic acids can be used alone or in combination of two or more.

The dibasic acid is preferably an aliphatic dibasic acid, and more preferably adipic acid.

Examples of the diprotic acid alkyl ester include the above-mentioned dibasic acid methyl ester and ethyl ester.

These dibasic acid alkyl esters can be used alone or in combination of two or more.

Examples of the dihydric alcohol include the above-mentioned low molecular weight diols. These dihydric alcohols can be used alone or in combination of two or more.

As the dihydric alcohol, an aliphatic diol is preferably used, and 3-methyl-1,5-pentanediol is more preferable.

Then, the polyester diol is obtained as a reaction product by a condensation reaction between the above-mentioned dibasic acid and the above-mentioned dihydric alcohol, or a transesterification reaction between the above-mentioned alkyl ester of the dibasic acid and the above-mentioned dihydric alcohol. Be done. The polyester diol preferably includes a reaction product obtained by a condensation reaction between a dibasic acid and a dihydric alcohol.

If necessary, the condensation reaction or transesterification reaction can be carried out under known catalysts and under known reaction conditions.

The hydroxyl value of the polyester diol is, for example, 65 mgKOH / g or more, preferably 100 mgKOH / g or more, more preferably 105 mgKOH / g or more, still more preferably 150 mgKOH / g or more, for example, 500 mgKOH / g or less, preferably 500 mgKOH / g or more. Is 300 mgKOH / g or less, more preferably 290 mgKOH / g or less, still more preferably 250 mgKOH / g or less.

When the hydroxyl value of the polyester diol is within the above range, the design and mechanical strength of the polyurethane resin can be improved.

The number average molecular weight of the polyester diol is, for example, 300 or more, preferably 400 or more, and for example, 1200 or less, preferably 1000 or less.

The diol is preferably the polyoxyalkylene diol and / or the polyester diol, and more preferably the combined use of the polyoxyalkylene diol and the polyester diol.

By using such a diol, the design and mechanical strength of the polyurethane resin can be improved.

The hydroxyl value of the diol is, for example, 65 mgKOH / g or more, preferably 100 mgKOH / g or more, more preferably 105 mgKOH / g or more, still more preferably 150 mgKOH / g or more, for example, 500 mgKOH / g or less, preferably 500 mgKOH / g or more. , 300 mgKOH / g or less, more preferably 290 mgKOH / g or less, still more preferably 250 mgKOH / g or less.

The number average molecular weight of the diol is, for example, 300 or more, preferably 400 or more, more preferably 500 or more, and for example, 1200 or less, preferably 1000 or less.

Examples of the triol include polyether triol, polyester triol, polycarbonate triol, polyurethane triol and the like. These triols can be used alone or in combination of two or more.

Preferred triols include polyether triol and polyester triol.

Examples of the polyether triol include polyoxyalkylene triol having an oxyalkylene group having 2 to 3 carbon atoms and polyoxyalkylene triol having an oxyalkylene group having 4 or more carbon atoms (polytetramethylene ether triol and the like). Can be mentioned. These polyether triols can be used alone or in combination of two or more.

As the polyether triol, preferably, a polyoxyalkylene triol having 2 to 3 carbon atoms in the oxyalkylene group can be mentioned.

Examples of the polyoxyalkylene triol having an oxyalkylene group having 2 to 3 carbon atoms include an addition polymer of an alkylene oxide having 2 to 3 carbon atoms (two or more kinds) using a low molecular weight triol, a low molecular weight triamine, or the like as an initiator. (Including random and / or block copolymers of alkylene oxides).

A low molecular weight triol is a trifunctional low molecular weight polyol having three hydroxyl groups, typically 40 or more, with a number average molecular weight of less than 400 (preferably less than 300).

Examples of low molecular weight triols include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, and trimethylolethane. , Trimethylolethane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3- (hydroxymethyl) pentane, 2,2-bis (hydroxymethyl) -3-butanol and others Aliphatic triol (8 to 24 carbon atoms) and the like, preferably trimethylolethane.

These low molecular weight triols can be used alone or in combination of two or more.

A low molecular weight triamine is a compound having three amino groups having a number average molecular weight of less than 300 (preferably less than 400), usually 40 or more, and is, for example, diethylenetriamine, 4-aminomethyl-1,8-octanediamine. , 2,2', 2''-triaminotriethylamine, tris-1,1,1-aminoethylethane, 1,2,3-triaminopropane, tris- (3-aminopropyl) -amine, N, N , N', N'-tetrax- (2-aminoethyl) -ethylenediamine and the like.

These low molecular weight triamines can be used alone or in combination of two or more.

Preferred examples of the initiator include low molecular weight triol.

Examples of the alkylene oxide having 2 to 3 carbon atoms include the above-mentioned alkylene oxide.

These alkylene oxides can be used alone or in combination of two or more.

Examples of the alkylene oxide are preferably ethylene oxide and propylene oxide, and more preferably propylene oxide.

Specific examples of such polyoxyalkylene triol include polyoxyethylene triol, polyoxypropylene triol, and propylene oxide-ethylene oxide copolymer triol (random and / or block copolymer).

These polyoxyalkylene triols can be used alone or in combination of two or more.

Preferred examples of the polyoxyalkylene triol include polyoxypropylene triol.

The hydroxyl value of polyoxyalkylene triol is, for example, 65 mgKOH / g or more, preferably 100 mgKOH / g or more, more preferably 109 mgKOH / g or more, still more preferably 150 mgKOH / g or more, still more preferably 300 mgKOH / g or more. More preferably 450 mgKOH / g or more, particularly preferably 500 mgKOH / g or more, for example, 800 mgKOH / g or more, preferably 600 mgKOH / g or less, more preferably 590 mgKOH / g or less, still more preferably 570 mgKOH. It is less than / g.

When the hydroxyl value of the polyoxyalkylene triol is within the above range, the design and mechanical strength of the polyurethane resin can be improved.

The number average molecular weight of polyoxyalkylene triol is, for example, 200 or more, preferably 250 or more, and for example, 2000 or less, preferably 1000 or less, and more preferably 500 or less.

The CPR (controlled polymerization rate) of the polyoxyalkylene triol is, for example, 5 or less, preferably 3 or less, more preferably 2 or less, still more preferably 1 or less, for example, 0 or more, preferably 1, It is 0.01 or more, more preferably 0.1 or more.

Examples of the polyester triol include polyester triol, which is a reaction product of a polybasic acid and / or an alkyl ester thereof and a polyhydric alcohol.

More specifically, polyester triols include, for example, reaction products of dibasic acids and / or alkyl esters thereof with trihydric alcohols and dihydric alcohols.

Examples of the dibasic acid and / or its alkyl ester include the above-mentioned dibasic acid and / or its alkyl ester. These polybasic acids and / or alkyl esters thereof can be used alone or in combination of two or more.

Examples of the dihydric alcohol include the above-mentioned divalent alcohol, and specific examples thereof include the above-mentioned low molecular weight diol. These dihydric alcohols can be used alone or in combination of two or more.

Examples of the trihydric alcohol include the above-mentioned low molecular weight triol. These trihydric alcohols can be used alone or in combination of two or more.

Then, in the polyester triol, for example, first, the above-mentioned dibasic acid and the above-mentioned trihydric alcohol are subjected to a condensation reaction at a ratio in which the carboxyl group of the dibasic acid is excessive with respect to the hydroxyl group of the trihydric alcohol, and then, after that, The obtained reaction product (reaction solution) is further reacted with a dihydric alcohol, or the above-mentioned alkyl ester of dibasic acid and the above-mentioned trihydric alcohol are combined with the alkyl ester group of the alkyl ester of dibasic acid. Is subjected to an ester exchange reaction in an excess ratio with respect to the hydroxyl group of the trihydric alcohol, and then the obtained reaction product (reaction solution) is further reacted with the dihydric alcohol to obtain a reaction product.

If necessary, the condensation reaction or transesterification reaction can be carried out under known catalysts and under known reaction conditions.

The hydroxyl value of the polyester triol is, for example, 65 mgKOH / g or more, preferably 100 mgKOH / g or more, more preferably 109 mgKOH / g or more, still more preferably 150 mgKOH / g or more, still more preferably 300 mgKOH / g or more, and further. It is preferably 450 mgKOH / g or more, particularly preferably 500 mgKOH / g or more, for example, 800 mgKOH / g or more, preferably 600 mgKOH / g or less, more preferably 590 mgKOH / g or less, still more preferably 570 mgKOH / g. It is as follows.

When the hydroxyl value of the polyester triol is within the above range, the design and mechanical strength of the polyurethane resin can be improved.

The number average molecular weight of the polyester triol is, for example, 200 or more, preferably 250 or more, and for example, 2000 or less, preferably 1000 or less, and more preferably 500 or less.

It should be noted that preferably, the polyester diol and the polyester triol are reaction products of a polybasic acid and / or an alkyl ester thereof and a polyhydric alcohol. That is, it is preferable that the polyester polyol (polycaprolactone polyol, polyvalerolactone polyol, etc.) obtained by ring-opening polymerization of lactones and lactides using a low molecular weight polyol as an initiator is not contained.

By using a reaction product of a polybasic acid and / or an alkyl ester thereof and a polyhydric alcohol instead of a ring-opening polymerization type polyester polyol as the polyester diol and the polyester triol, it is possible to improve the design and mechanical strength. it can.

The triol is preferably the polyoxyalkylene triol and / or the polyester triol, and more preferably the polyoxyalkylene triol.

By using such triol, the design and mechanical strength of the polyurethane resin can be improved.

The hydroxyl value of triol is, for example, 65 mgKOH / g or more, preferably 100 mgKOH / g or more, more preferably 109 mgKOH / g or more, still more preferably 150 mgKOH / g or more, still more preferably 300 mgKOH / g or more, still more preferable. Is 450 mgKOH / g or more, particularly preferably 500 mgKOH / g or more, for example, 800 mgKOH / g or more, preferably 600 mgKOH / g or less, more preferably 590 mgKOH / g or less, still more preferably 570 mgKOH / g or less. Is.

When the hydroxyl value of triol is within the above range, the design and mechanical strength of the polyurethane resin can be improved.

The number average molecular weight of triol is, for example, 200 or more, preferably 250 or more, and for example, 2000 or less, preferably 1000 or less, and more preferably 500 or less.

Then, the polyol component preferably contains more hydroxyl groups derived from diol than hydroxyl groups derived from triol. In other words, preferably, the chemical equivalent of diol contained in the polyol component (mass of diol / hydroxyl equivalent of diol) is higher than the chemical equivalent of triol contained in the polyol component (mass of triol / hydroxyl equivalent of triol). There are many.

The hydroxyl group equivalent is calculated by the following formula (the same applies hereinafter).

Equivalent to hydroxyl groups = 56100 / hydroxyl value More specifically, the content ratio of the triol (based on chemical equivalents) to the total amount of polyol components is, for example, 1 equivalent% or more, preferably 3 equivalents or more, more preferably. Is 5 equivalents or more, more preferably 6 equivalents or more, still more preferably 7 equivalents or more, still more preferably 10 equivalents or more, still more preferably 20 equivalents or more, still more preferably 25 equivalents%. The above is particularly preferably 30 equivalent% or more, for example, 90 equivalent% or less, preferably 80 equivalent% or less, more preferably 70 equivalent% or less, still more preferably 60 equivalent% or less, still more preferably. It is 50 equivalents or less, more preferably less than 50 equivalents, and particularly preferably 45 equivalents or less.

Further, the content ratio of the diol (based on the chemical equivalent) is, for example, 10 equivalent% or more, preferably 20 equivalent% or more, more preferably 30 equivalent% or more, still more preferably 30 equivalent% or more, based on the total amount of the polyol component. 40 equivalent% or more, more preferably 50 equivalent% or more, still more preferably more than 50 equivalent%, particularly preferably 55 equivalent% or more, for example 99 equivalent% or less, preferably 97 equivalent% or less. More preferably 95 equivalents or less, still more preferably 94 equivalents or less, still more preferably 93 equivalents or less, still more preferably 90 equivalents or less, still more preferably 80 equivalents or less, still more preferably. 75 equivalent% or less, particularly preferably 70 equivalent% or less.

On a mass basis, the content ratio of the triol (based on mass) is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and further, based on the total amount of the polyol components. It is preferably 6% by mass or more, more preferably 7% by mass or more, still more preferably 8% by mass or more, still more preferably 10% by mass or more, still more preferably 13% by mass or more, and particularly preferably 15% by mass. % Or more, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably. , Less than 30% by mass, particularly preferably 25% by mass or less.

Further, the content ratio (mass basis) of the diol is, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60, based on the total amount of the polyol components. Mass% or more, more preferably 70% by mass or more, still more preferably more than 70% by mass, particularly preferably 75% by mass or more, for example, 99% by mass or less, preferably 97% by mass or less. More preferably 95% by mass or less, still more preferably 94% by mass or less, still more preferably 93% by mass or less, still more preferably 92% by mass or less, still more preferably 90% by mass or less, still more preferably 87. By mass or less, particularly preferably 85% by mass or less.

When the content ratio of triol and the content ratio of diol are within the above ranges, the design and mechanical strength of the polyurethane resin can be improved.

The CPR (controlled polymerization rate) of the polyol component is, for example, 5 or less, preferably 3 or less, and for example, 0 or more, preferably 0.01 or more, and more preferably 0.1 or more.

When the CPR exceeds the above upper limit, that is, when the polyol component contains an excessively large amount of a basic substance acting as a urethanization catalyst, the reaction rate between the polyisocyanate component and the polyol component may become excessively high. Therefore, local crystallization may occur in the obtained polyurethane resin, and as a result, the design of the polyurethane resin may be deteriorated.

On the other hand, when the CPR is excessively low, that is, when the content of the basic substance acting as a urethanization catalyst is excessively low, the reaction rate between the polyisocyanate component and the polyol component becomes relatively slow, so that it is local. Crystallization can be suppressed and designability can be ensured, but the crosslink density may decrease and the mechanical strength (hardness, etc.) may decrease.

In this regard, if the CPR is within the above range, the reaction rate between the polyisocyanate component and the polyol component can be adjusted to an appropriate range, so that local crystallization can be suppressed and sufficient cross-linking can be performed. Since the density can be ensured, it is possible to obtain a polyurethane resin having excellent design and mechanical strength.

In addition, the polyol component preferably contains a polyester diol and / or a polyester triol.

That is, the polyol component may contain only the polyether component (polyoxyalkylene diol and / or polyoxyalkylene triol), but preferably contains the polyester component (polyester diol and / or polyester triol).

When a polyester diol and / or a polyester triol is used, the total content of the polyester diol and the polyester triol (based on the chemical equivalent) in the polyol component is, for example, 3 equivalent% or more, preferably 5 equivalent% or more, more preferably. Is 10 equivalent% or more, more preferably 15 equivalent% or more, for example, 70 equivalent% or less, preferably 65 equivalent% or less, more preferably 60 equivalent%, still more preferably 50 equivalent% or less.

When the content ratios of the polyester diol and the polyester triol are within the above ranges, the hardness, mechanical strength and heat resistance of the polyurethane resin can be improved.

In the following, the total amount of polyester diol and polyester triol content ratio (based on chemical equivalent) with respect to the polyol component may be referred to as ester equivalent (equivalent%).

Further, the polyol component can further contain a polyol other than the above diol and the above triol (hereinafter, referred to as other polyol).

Examples of other polyols include known high molecular weight polyols having a number average molecular weight of 300 or more and 5000 or less. Specifically, for example, polycarbonate polyols, acrylic polyols, epoxy polyols, natural oil polyols, silicone polyols, and fluorine. Examples thereof include polyols, polyolefin polyols, and polyurethane polyols.

In addition to the above, other polyols include, for example, a diol having a hydroxyl value less than the lower limit, a diol having a hydroxyl value exceeding the upper limit, a triol having a hydroxyl value less than the lower limit, or a hydroxyl value having the upper limit. Examples include excess triol, and further examples include low molecular weight polyols having a number average molecular weight of less than 300 (preferably less than 400), usually 40 or more and having 4 or more hydroxyl groups.

These other polyols can be used alone or in combination of two or more.

The content ratio of other polyols (based on chemical equivalents) is 10 equivalents or less, preferably 5 equivalents or less, and more preferably 0 equivalents, based on the total amount of the polyol components.

Then, the polyol component is adjusted so that the hydroxyl value as a whole is within a predetermined range.

More specifically, the hydroxyl value of the polyol component is 30 mgKOH / g or more, preferably 100 mgKOH / g or more, more preferably 150 mgKOH / g or more, still more preferably 200 mgKOH / g or more, and 1200 mgKOH / g or less. It is preferably 1000 mgKOH / g or less, more preferably 600 mgKOH / g or less, and even more preferably 300 mgKOH / g or less.

The average number of functional groups of the polyol component is, for example, 2.1 or more, preferably 2.2 or more, more preferably 2.3 or more, still more preferably 2.4 or more, and for example, 2.9. Hereinafter, it is preferably 2.8 or less, more preferably 2.7 or less, and further preferably 2.6 or less. When the average number of functional groups of the polyol component is within the above range, the hardness, mechanical strength, heat resistance and moisture heat resistance of the polyurethane resin can be improved.

In addition, the polyurethane resin composition can contain a urethanization catalyst in an appropriate ratio, if necessary.

Examples of the urethanization catalyst include amines and organometallic compounds.

Examples of amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether and N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, for example, imidazole. Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.

Examples of the organic metal compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate, and dibutyltin. Organic tin compounds such as dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, dibutyltin dichloride, eg organic lead compounds such as lead octanate, lead naphthenate, eg organic nickel compounds such as nickel naphthenate, For example, an organic cobalt compound such as cobalt naphthenate, for example, an organic copper compound such as copper octate, for example, an organic bismuth compound such as bismuth octylate, bismuth neodecanoate, an organic zinc compound, an organic zirconium compound, zinc acetylacetonate, Examples thereof include bismuth (2-ethylhexanoate), bismuth neodecanoate, zinc 2-ethylhexanoate, zinc neodecanoate, bismuth tetramethylheptandioate, and mixtures thereof.

Further, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate and potassium octylate.

In addition, examples of the urethanization catalyst include compounds containing zinc and zirconium, zirconium compounds, and the like.

Such a urethanization catalyst is available as a commercial product, and as a compound containing zinc and zirconium, for example, trade name: K-Kat XK-627 (manufactured by King Industries), trade name: K-Kat XK- Examples thereof include 604 (manufactured by King Industries), trade name: K-Kat XK-617 (manufactured by King Industries), and trade name: K-Kat XK-618 (manufactured by King Industries). Moreover, as a zirconium compound, a trade name: K-Kat XK-6212 (manufactured by King Industries) and the like can be mentioned.

The urethanization catalyst preferably includes a compound containing zinc and zirconium, and specifically, a trade name: K-Kat XK-627. By using such a urethanization catalyst, a good pot life is exhibited, and the mechanical properties of the obtained polyurethane resin are excellent. In addition, the obtained polyurethane resin has no sink marks and has a good appearance.

These urethanization catalysts can be used alone or in combination of two or more.

The amount of the urethanization catalyst added is preferably 10 ppm or more, preferably 20 ppm or more, more preferably 30 ppm or more, still more preferably 50 ppm or more, and particularly preferably 100 ppm or more, based on the total mass of the polyurethane resin. Yes, for example, 1000 ppm or less, preferably 750 ppm or less, more preferably 500 ppm or less, still more preferably 250 ppm or less, and particularly preferably 150 ppm or less.

Further, the polyurethane resin composition can further contain a known additive in an appropriate ratio.

Known additives include, for example, reaction retarders, stabilizers, mold release agents, fillers, shock-absorbing microparticles, hydrolysis inhibitors, dehydrators, flame retardants, defoamers, pigments, dyes, lubricants, plasticizers, etc. Examples include blocking agents.

Such a polyurethane resin composition is configured as, for example, a two-component resin material having an agent A containing a polyisocyanate component and an agent B containing a polyol component.

The urethanization catalyst and known additives may be contained in either agent A or agent B, but are preferably contained in agent B.

Then, in order to produce the polyurethane resin, the polyisocyanate component and the polyol component are reacted (urethaneization reaction) to cure the polyurethane resin composition. That is, the polyurethane resin contains a cured product of the polyurethane resin composition, and is preferably composed of a cured product of the polyurethane resin composition.

In the production of the polyurethane resin, for example, a known method such as a one-shot method or a prepolymer method is adopted.

In the one-shot method, for example, the polyisocyanate component and the polyol component are reacted at once.

The reaction temperature in the one-shot method is, for example, 25 ° C. (room temperature) or higher, preferably 25 ° C. (room temperature) or higher.
It is 35 ° C. or higher, for example, 200 ° C. or lower, preferably 100 ° C. or lower. The reaction time in the one-shot method is, for example, 5 minutes or more, preferably 10 minutes or more, for example, 72 hours or less, preferably 24 hours or less.

In the prepolymer method, for example, first, a polyisocyanate component and a part of a polyol component are reacted to synthesize an isocyanate group-terminated prepolymer having an isocyanate group at the molecular terminal. The resulting isocyanate group-terminated prepolymer is then reacted with the rest of the polyol component.

The reaction temperature in the synthesis of the isocyanate group-terminated prepolymer is, for example, 25 ° C. (room temperature) or higher, preferably 50 ° C. or higher, for example, 150 ° C. or lower, preferably 120 ° C. or lower. The reaction time in the synthesis of the isocyanate group-terminated prepolymer is, for example, 0.5 hours or more, preferably 2 hours or more, for example, 18 hours or less, preferably 10 hours or less.

Further, the range of the reaction temperature between the isocyanate group-terminated prepolymer and the polyol component is the same as the range of the reaction temperature in the one-shot method, and the range of the reaction time between the isocyanate group-terminated prepolymer and the polyol component is, for example. , The range of reaction time in the one-shot method is the same.

In the production of the polyurethane resin, for example, bulk polymerization or solution polymerization can be adopted.

Then, the fiber reinforced plastic is produced, for example, by impregnating the above-mentioned polyurethane resin composition with the above-mentioned base material and curing it.

More specifically, as a method for producing a fiber reinforced plastic, for example, an RTM (Resin Transfer Molding) method, an HP-RTM (High-Pressure Resin Transfer Molding) method, a WCM (Wet Compression Molding) method, and a RIM (Reaction Molding) method. ) Method, prepreg method, hand lay-up method, filament winding method, pull-fusion method and the like.

Among the methods for producing fiber reinforced plastics, the RTM method, the HP-RTM method, the WCM method, and / or the RIM method are preferably adopted. In other words, the fiber reinforced plastic is preferably produced by the RTM method, the HP-RTM method, the WCM method, and / or the RIM method.

In the RTM method and the RIM method, a base material made of a woven fabric containing reinforcing fibers is cut and molded in advance according to the inner dimensions of the mold, and placed in the mold (arrangement step). In addition, the mold is heated to the above-mentioned preheating temperature.

Next, the above polyurethane resin composition is cast into the mold (casting step). More specifically, the polyisocyanate component (agent A) and the polyol component (agent B) are mixed and then injected into a preheated mold to impregnate the substrate with the polyurethane resin composition.

Then, the polyurethane resin composition is reacted and cured under the above conditions (curing step).

Further, in the HP-RTM method, in the above RTM method, the inside of the mold is depressurized, and the pressurized polyurethane resin composition (agent A and agent B) is injected into the mold at high speed to impregnate the base material, and the above. Cure under conditions. Specifically, it is the production method described in Japanese Patent Application Laid-Open No. 2015-533352.

In the WCM method, in the above HP-RTM method, the mixed polyurethane resin composition (agent A and agent B) is applied and impregnated on the base material arranged in the mold without depressurizing the inside of the mold. Cure under conditions.

As described above, the polyurethane resin composition impregnated in the base material is cured, and a fiber reinforced plastic containing the base material and the polyurethane resin is produced.

In the fiber reinforced plastic, the content ratio of the base material (fiber volume content (Vf)) on a volume basis is, for example, 20% by volume or more, preferably 30% by volume or more, based on the total volume of the fiber reinforced plastic. For example, it is 70% by volume or less, preferably 60% by volume or less.

The content ratio of the polyurethane resin (resin volume content) on a volume basis is, for example, 30% by volume or more, preferably 40% by volume or more, for example, 80% by volume or less, based on the total volume of the fiber reinforced plastic. , Preferably 70% by volume or less.

The fiber volume content can be calculated from the formula "(reinforcing fiber mass ÷ reinforcing fiber density) ÷ mold volume", and the resin volume content can be calculated from the formula "100-fiber volume content".

Further, in the fiber reinforced plastic, the content ratio of the base material (fiber mass content) on a mass basis is, for example, 27% by mass or more, preferably 39% by mass or more, for example, with respect to the total mass of the fiber reinforced plastic. , 86% by mass or less, preferably 78% by mass or less.

The content ratio of the polyurethane resin (resin mass content) on a mass basis is, for example, 14% by mass or more, preferably 22% by mass or more, for example, 73% by mass or less, based on the total mass of the fiber reinforced plastic. , Preferably 61% by mass or less.

The resin mass content can be calculated from the formula "((1-Vf) x resin density) ÷ (Vf x reinforcing fiber density + (1-Vf) x resin density)", and the fiber mass content is "100-". It can be calculated from the formula of "resin mass content".

In such a fiber-reinforced plastic, a polyurethane resin which is a reaction product of a polyisocyanate component containing an aliphatic polyisocyanate and / or a derivative thereof and a polyol component having a hydroxyl value of 30 mgKOH / g or more and 1200 mgKOH / g or less is produced. Used.

Since the above polyurethane resin has excellent followability to the base material, when the base material is a woven fabric containing reinforcing fibers, the fibers have a woven fabric-derived design (unevenness, etc.) regardless of the mold. Can be applied to reinforced plastics.

Therefore, the above-mentioned fiber-reinforced plastic and the method for producing the fiber-reinforced plastic can improve the design, and can further reduce the labor and cost.

Since the above-mentioned fiber reinforced plastic has excellent designability, it is provided on the outermost surface of various products. The present invention also includes an article (fiber reinforced plastic article) having the above-mentioned fiber reinforced plastic on the outermost surface.

The fiber reinforced plastic article is not particularly limited, and examples thereof include an article made of fiber reinforced plastic used in various industrial fields.

More specifically, fiber reinforced plastics and fiber reinforced plastic articles include, for example, members of vehicles (automobiles, aircraft, motorcycles, bicycles) (eg, structural members, interior materials, exterior materials, wheels, spokes, seat tables). Etc.), it is preferably used.

In addition to the above, fiber reinforced plastics include, for example, outer shell material of helmet, robot member, ship member, yacht member, rocket member, office use, healthcare member (nursing prosthesis, nursing use, bed, eye). (Wear frames, etc.), structural materials for wearable materials, sports equipment (golf club shafts, tennis racket frames, ski boards, snowboards, etc.), amusement materials (jet coasters, etc.), building materials for buildings and houses, paper rolls , Electronic parts (smartphones, tablets, etc.) housings, power generation devices (thermal power generation, hydroelectric power generation, wind power generation, nuclear power generation) structures, tank lorries and other structures.

Next, the present invention will be described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are the compounding ratios corresponding to those described in the above-mentioned "Form for carrying out the invention". Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, parameter, etc. be able to.

In addition, the measurement methods adopted in each preparation example, each synthesis example, each production example, each example, and each comparative example are described below.

1. 1. Measurement method <Concentration of pentamethylene diisocyanate (unit: mass%)>
A chromatogram obtained under the following HPLC analysis conditions using pentamethylene diisocyanate (hereinafter abbreviated as PDI) produced in the same manner as in Example 1 in the specification of International Publication No. 2012/121291. The concentration of pentamethylene diisocyanate in the polyisocyanate derivative was calculated from the calibration curve prepared from the area value.

Equipment; Prominence (manufactured by Shimadzu Corporation)
1) Pump LC-20AT
2) Degassa DGU-20A3
3) Autosampler SIL-20A
4) Column constant temperature bath COT-20A
5) Detector SPD-20A
Column; SHISEIDO SILICA SG-120
Column temperature; 40 ° C
Eluent; n-hexane / methanol / 1,2-dichloroethane = 90/5/5 (volume ratio)
Flow rate; 0.2 mL / min
Detection method; UV 225 nm
<Isocyanate group content (unit: mass%)>
The isocyanate group content of the polyisocyanate derivative was measured by a n-dibutylamine method based on JIS K-1556 (2006) using a potentiometric titrator.

<Content ratio of allophanate group to isocyanurate group>
¹ H-NMR was measured under the following equipment and conditions, and the content ratio of allophanate group to 100 mol of isocyanurate group was measured from the integrated value of each peak.

Tetramethylsilane was used as a reference for the chemical shift of 0 ppm.
Equipment: JNM-AL400 (manufactured by JEOL)
Conditions: Measurement frequency: 400 MHz, solvent: DMSO, concentration: 5%
Measurement temperature: Room temperature, 128 scans Pulse interval: 15 seconds Peak range of allophanate groups: 8.3 to 8.7 ppm
Peak range of isocyanurate groups: 3.8 ppm
<CPR>
CPR was measured by a method conforming to JIS K1557-4 (2007).

2. Raw material (1) Polyisocyanate component Preparation example 1 (aliphatic polyisocyanate derivative A)
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 500 parts by mass of PDI produced in the same manner as in Example 1 in the specification of International Publication No. 2012/121291. 5 parts by mass of isobutyl alcohol, 0.3 parts by mass of 2,6-di (tert-butyl) -4-methylphenol, and 0.3 parts by mass of tris (tridecyl) phosphite were charged, and the temperature was 80 ° C. for 2 hours. It was reacted.

Then, 0.05 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was added as an isocyanurate-forming catalyst. The refractive index and the purity of isocyanate were measured, and the reaction was continued until a predetermined isocyanate group conversion rate was reached. Since the predetermined isocyanate group conversion rate (10% by mass) was reached after 50 minutes, 0.12 parts by mass of o-toluenesulfonamide was added. The obtained reaction solution was passed through a thin film distillation apparatus (vacuum degree 0.093 KPa, temperature 150 ° C.) to remove unreacted pentamethylene diisocyanate, and further, o- was added to 100 parts by mass of the obtained composition. 0.02 parts by mass of toluene sulfonamide was added to obtain an aliphatic polyisocyanate derivative A.

The concentration of pentamethylene diisocyanate (unreacted monomer) of this aliphatic polyisocyanate derivative A is 0.5% by mass, the content of isocyanate groups is 23.5% by mass, and the content of allophanate groups is 54 with respect to 100 mol of isocyanurate groups. It was 0.7 mol.

Preparation Example 2 (aliphatic polyisocyanate derivative B)
The aliphatic polyisocyanate derivative B was obtained by the same method as in Preparation Example 1 except that 500 parts by mass of IPDI was used instead of 500 parts by mass of PDI.

Preparation Example 3 (Aromatic Polyisocyanate Derivative C)
Cosmonate M-200 (manufactured by Mitsui Chemicals, polymethylene polyphenyl isocyanate having an isocyanate group content of 31.6% by mass, molar ratio of isocyanate groups of diphenylmethane diisocyanate to all isocyanate groups of polymethylene polyphenyl polyisocyanate: 42.8 mol %) Was prepared as an aromatic polyisocyanate derivative C.

Preparation Example 4 (Aromatic Polyisocyanate Derivative D)
Cosmonate LK (manufactured by Mitsui Chemicals, carbodiimide derivative of polymethylene polyisocyanate having an isocyanate group content of 28.2% by mass, carbodiimide derivative content of 30% by mass, diphenylmethanediisocyanate in the total isocyanate group of the carbodiimide derivative of polymethylene polyisocyanate The molar ratio of isocyanate groups = 83.5 mol%) was prepared as the aromatic polyisocyanate derivative D.

(2) polyol component The following raw materials were prepared.
<Diol>
P-510: Trade name "Clare polyol P-510", polyester diol (reaction product obtained by condensation reaction of 3-methyl-1,5-pentanediol with adipic acid), average hydroxyl value 224 mgKOH / g , Average number of functional groups 2, hydroxyl group equivalent 250, Diol-280 manufactured by Kuraray Co., Ltd .: trade name "Actcol Diol-280", polyoxyalkylene diol (polyoxypropylene diol), average hydroxyl value 400 mgKOH / g, average number of functional groups 2, Hydroxyl equivalent 140, number average molecular weight 281, manufactured by Mitsui Chemicals, Inc. 6PN: trade name "bisol 6PN", polyoxyalkylene diol (reaction product of bisphenol A and propylene oxide), average hydroxyl group 198 mgKOH / g, average number of functional groups 2, hydroxyl group Equivalent amount 283, manufactured by Toho Chemical Industry Co., Ltd. <Triol>
T-300: Trade name "Actcol T-300", polyoxyalkylene (2 to 3 carbon atoms) triol (polyoxypropylene triol), average hydroxyl value 561 mgKOH / g, average functional group number 3, hydroxyl group equivalent 100, CPR0. 1. Mitsui Chemicals SKC Polyurethane Co., Ltd. 3. Production of fiber reinforced plastic Example 1
That is, first, in a metal casting mold having a thickness of 2.6 mm, two layers of carbon fiber woven fabric (twill weave type woven fabric (3K twill woven fabric) with 3000 fibers) and twill weave type with 12,000 fibers as a base material. Three layers of woven fabric (12K twill woven fabric) and a laminated body in which 3K / 12K / 12K / 12K / 3K were laminated in this order) were allowed to stand (arrangement step). The upper and lower surfaces inside the metal casting mold were flat.

Next, a polyurethane resin composition was prepared by the following method and cast into a metal casting mold (casting step).

More specifically, P-510 is 50.0 parts by mass, T-300 is 20.0 parts by mass, 6PN is 30.0 parts by mass, and Irganox 245 (hindered phenolic antioxidant, BASF). (Manufactured by Japan) was uniformly mixed with 0.2 parts by mass at 50 ° C. to obtain a polyol component.

Next, 0.01 parts by mass of K-Kat XK-627 (urethane catalyst, manufactured by King Industries) and 0.002 parts by mass of BYK A535 (antifoaming agent, manufactured by Big Chemie Japan) were added to the polyol component. , 50 ° C. was mixed uniformly. This was designated as Agent B.

Further, an aliphatic polyisocyanate derivative A (Preparation Example 1) was prepared as an agent A as a polyisocyanate component.

Then, the agent A and the agent B were mixed so that the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the polyol component was 1.0, and defoamed under reduced pressure.

As a result, a polyurethane resin composition was prepared as a mixture of the agent A and the agent B.

Then, the polyurethane resin composition was poured into a metal casting mold in which the above-mentioned carbon fiber woven fabric was arranged.

Then, it was heated at 100 degreeC for 30 minutes, and the polyurethane resin composition was reacted and cured (curing step).

As a result, a polyurethane resin was formed as a cured product of the polyurethane resin composition, and a fiber-reinforced plastic comprising a carbon fiber woven fabric (base material) and a polyurethane resin impregnated in the carbon fiber woven fabric was obtained.

Example 2 and Comparative Example 2
A fiber reinforced plastic was obtained in the same manner as in Example 1 except that the formulation was changed to that shown in Table 1.

Comparative Example 1
Diol-280 is 100 parts by mass, picolinic acid (reaction retarder) is 0.6 parts by mass, K-13 (nurateization catalyst) is 1.0 part by mass, and SCAT-24 (urethaneization catalyst) is 0. .1 part by mass was uniformly mixed at 40 ° C. to obtain a polyol component. This was designated as Agent B.

Further, 95.1 parts by mass of the aromatic polyisocyanate derivative C and 104.9 parts by mass of the aromatic polyisocyanate derivative D were uniformly mixed at 40 ° C. to obtain a polyisocyanate component. This was designated as Agent A.

Then, the agents A and B were mixed so that the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the polyol component was 2.0, and defoaming was performed under reduced pressure.

As a result, a polyurethane resin composition was prepared as a mixture of the agent A and the agent B.

Then, the polyurethane resin composition was poured into a metal casting mold prepared in the same manner as in Example 1.

Then, it was heated at 80 degreeC for 3 minutes, and the polyurethane resin composition was reacted and cured (curing step).

As a result, a fiber reinforced plastic was obtained.

4. Evaluation The fiber reinforced plastic was evaluated by the following method. The results are shown in Table 1.

(1) Designability (woven fabric followability)
The fiber reinforced plastic was magnified 20 times with an optical microscope and photographed in 3D photographing mode. Then, from the obtained photograph, the woven fabric-derived design (unevenness) is sufficiently imparted to the surface of the fiber reinforced plastic, and the unevenness can be seen immediately by touching it with a finger (○), or it is imparted to some extent. It was evaluated whether the unevenness can be seen by touching it with a finger (Δ), or whether the design (unevenness) derived from the woven fabric is not sufficiently imparted and the unevenness cannot be confirmed with a finger (x).

As a result, in the fiber-reinforced plastic of Example 1, the polyurethane resin followed the carbon fiber woven fabric, and the woven fabric-derived design (unevenness) was sufficiently imparted.

Further, in the fiber-reinforced plastic of Example 2, the polyurethane resin follows the carbon fiber woven fabric, and the woven fabric-derived design (unevenness) is imparted to some extent.

On the other hand, in the fiber-reinforced plastics of Comparative Examples 1 and 2, the polyurethane resin did not have sufficient followability to the carbon fiber woven fabric, and the woven fabric-derived design (unevenness) was not sufficiently imparted.

A photograph of the fiber reinforced plastic of Example 1 is shown in FIG. 1, and a photograph of the fiber reinforced plastic of Comparative Example 1 is shown in FIG.

(2) Fiber Volume Content In fiber reinforced plastics, the fiber content (Vf) per unit volume was calculated by the following method.

First, the mass of the reinforcing fibers (carbon fiber, density 1.8 g / cm ³ ) used in the production of fiber reinforced plastic was measured. In Example 1, it was 197 g.

On the other hand, the volume of the mold used in the production of fiber reinforced plastic was determined. In Example 1, length × width × thickness = 30 cm × 30 cm × 0.26 cm = 234 cm ³ .

Then, assuming that this mold volume is equivalent to the volume of the fiber reinforced plastic assuming that there is no grain, the fiber volume content is calculated by the following formula.

(Reinforced fiber mass ÷ Reinforced fiber density) ÷ Mold volume

Claims (12)

A base material and a polyurethane resin impregnated in the base material are provided.
The base material is a woven fabric containing reinforcing fibers.
The polyurethane resin is
Polyisocyanate components containing aliphatic polyisocyanates and / or derivatives thereof, and
A fiber-reinforced plastic characterized by being a reaction product with a polyol component having a hydroxyl value of 30 mgKOH / g or more and 1200 mgKOH / g or less. The polyisocyanate component contains a derivative of an aliphatic polyisocyanate and contains
The derivative of the aliphatic polyisocyanate has an isocyanurate group and an allophanate group, and the content ratio of the allophanate group is 10 mol or more and 90 mol or less with respect to 100 mol of the isocyanurate group. Item 1. The fiber reinforced plastic according to Item 1. The polyol component is
Triol with a hydroxyl value of 100 mgKOH / g or more and 600 mgKOH / g or less,
It contains a diol having a hydroxyl value of 100 mgKOH / g or more and 300 mgKOH / g or less.
The triol is
Polyoxyalkylene triol having 2-3 carbon atoms in the oxyalkylene group and / or
Polyester triol, which is a reaction product of a polybasic acid and / or an alkyl ester thereof and a polyhydric alcohol.
The diol is
Polyoxyalkylene diols having 2-3 carbon atoms in the oxyalkylene group and / or
The fiber-reinforced plastic according to claim 1 or 2, wherein the polyester diol is a reaction product of a dibasic acid and / or an alkyl ester thereof and a dihydric alcohol. The fiber-reinforced plastic according to any one of claims 1 to 3, wherein the aliphatic polyisocyanate contains pentamethylene diisocyanate. The content ratio of the triol is 60 equivalent% or more and 95 equivalent% or less with respect to the total amount of the polyol component.
The fiber-reinforced plastic according to claim 3 or 4, wherein the content ratio of the diol is 5 equivalent% or more and 40 equivalent% or less. The fiber-reinforced plastic according to any one of claims 1 to 5, wherein the reinforcing fiber is a carbon fiber. The fiber-reinforced plastic according to any one of claims 1 to 6, wherein the ratio of the base material to the total volume of the fiber-reinforced plastic is 30% by volume or more and 60% by volume or less. .. A fiber-reinforced plastic article comprising the fiber-reinforced plastic according to any one of claims 1 to 7 on the outermost surface. An arrangement process in which a base material made of a woven fabric containing reinforcing fibers is arranged in a mold, and
A polyurethane resin composition containing a polyisocyanate component containing an aliphatic polyisocyanate and / or a derivative thereof and a polyol component having a hydroxyl value of 30 mgKOH / g or more and 1200 mgKOH / g or less is cast into the mold. Casting process and
A method for producing a fiber reinforced plastic, which comprises a curing step of reacting and curing the polyurethane resin composition. The polyisocyanate component contains a derivative of an aliphatic polyisocyanate and contains
The derivative of the aliphatic polyisocyanate has an isocyanurate group and an allophanate group, and the content ratio of the allophanate group is 10 mol or more and 90 mol or less with respect to 100 mol of the isocyanurate group. Item 9. The method for producing a fiber reinforced plastic according to Item 9. The polyol component is
Triol with a hydroxyl value of 100 mgKOH / g or more and 600 mgKOH / g or less,
It contains a diol having a hydroxyl value of 100 mgKOH / g or more and 300 mgKOH / g or less.
The triol is
Polyoxyalkylene triol having 2-3 carbon atoms in the oxyalkylene group and / or
Polyester triol, which is a reaction product of a polybasic acid and / or an alkyl ester thereof and a polyhydric alcohol.
The diol is
Polyoxyalkylene diols having 2-3 carbon atoms in the oxyalkylene group and / or
The method for producing a fiber-reinforced plastic according to claim 9 or 10, wherein the polyester diol is a reaction product of a dibasic acid and / or an alkyl ester thereof and a dihydric alcohol. The fiber-reinforced plastic is produced by the RTM method, the HP-RTM method, the WCM method, and / or the RIM method.
The method for producing a fiber reinforced plastic according to any one of claims 9 to 11.