JP6660717B2 - Fiber reinforced composite material, material for automobile, aircraft and windmill blades - Google Patents

Description

  The present invention relates to a material member for a fiber reinforced composite material, an automobile, an aircraft, and a windmill blade.

  BACKGROUND ART In recent years, fiber-reinforced composite materials composed of various reinforcing fibers and a matrix resin have a light weight and a high toughness, and therefore, their use for blades of aircraft, automobiles, windmills and the like is rapidly progressing.

  As a matrix resin used for the fiber-reinforced composite material, a resin such as epoxy, urethane, polyamide, and phenol is used (for example, see Patent Documents 1, 2, and 3). Among them, urethane-based resins are widely used not only as matrix resins but also as paints, inks, adhesives, etc., because they exhibit excellent properties such as chemical resistance and abrasion resistance. In addition, when an aliphatic or alicyclic isocyanate is used as a raw material, good weather resistance can be imparted.

JP 2011-231414 A JP 2014-162858 A JP 2012-153109 A

  However, urethane-based resins have a decomposition temperature of urethane groups of about 150 to 250 ° C., and are not suitable for applications requiring high-temperature stability. Furthermore, corrosive gas permeability is high, and sufficient barrier property may not be exhibited in some cases. Therefore, application in applications requiring corrosive gas permeation prevention properties is limited.

  Accordingly, an object of the present invention is to provide a fiber-reinforced composite material having heat resistance and good anti-corrosive gas permeation resistance.

  The present inventors have repeatedly studied to solve the above-mentioned problems, and have obtained a fiber-reinforced composite using a polyisocyanate resin prepared from a polyisocyanate composition having a lower toxicity than an aliphatic or alicyclic diisocyanate as a raw material. It has been found that the above problem can be solved by using the material as a matrix resin.

  That is, the present invention is as follows.

[1]
Including reinforced fibers and matrix resin,
A fiber-reinforced composite material, wherein the matrix resin is a polyisocyanate resin obtained from at least one type of diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and having an isocyanurate structure as a unit structure.

[2]
The fiber-reinforced composite material according to [1], wherein the reinforcing fibers are at least one selected from the group consisting of carbon fibers and cellulose fibers.

[3]
The fiber-reinforced composite material according to [2], wherein the reinforcing fibers are carbon fibers.

[4]
In the polyisocyanate resin, the molar ratio of the isocyanurate group to the total of the urethane group and the urea group (isocyanurate group / (urethane group + urea group)) is 100/0 to 95/5, [1] to The fiber-reinforced composite material according to any one of [3].

[5]
The fiber reinforcement according to any one of [1] to [4], wherein the polyisocyanate resin has a molar ratio of isocyanurate groups to allophanate groups (isocyanurate groups / allophanate groups) of from 99/1 to 50/50. Composite materials.

[6]
An automobile material member using the fiber-reinforced composite material according to any one of [1] to [5].

[7]
An aircraft material member using the fiber-reinforced composite material according to any one of [1] to [5].

[8]
A material member for a wind turbine blade using the fiber-reinforced composite material according to any one of [1] to [5].

  The fiber reinforced composite material of the present invention has a heat resistance and a low corrosive gas permeability.

  Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. Note that the present invention is not limited to the following embodiment. The present invention can be appropriately modified and implemented within the scope of the invention.

≪Fiber reinforced composite material≫
The fiber-reinforced composite material of the present embodiment includes a reinforcing fiber and a matrix resin, and the matrix resin is a polyisocyanate resin. The fiber-reinforced composite material of the present embodiment also includes a prepreg.

≪Polyisocyanate resin≫
The polyisocyanate resin used in the present embodiment will be described in detail below.

  The polyisocyanate resin used in the present embodiment is obtained from at least one type of diisocyanate selected from the group consisting of aliphatic diisocyanate and alicyclic diisocyanate, and has an isocyanurate structure as a unit structure. In this embodiment, having an isocyanurate structure as a unit structure means that a resin is formed by three-dimensional crosslinking of the isocyanurate structure. The isocyanurate structure (hereinafter also referred to as “isocyanurate group”) is described in the following formula (1).

  In the present embodiment, the aliphatic diisocyanate is a diisocyanate having a saturated aliphatic group in the molecule, while the alicyclic diisocyanate is a diisocyanate having a cyclic aliphatic group in the molecule. The use of an aliphatic diisocyanate is more preferable because the resulting polyisocyanate resin can have flexibility. Examples of the aliphatic diisocyanate include, but are not particularly limited to, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (hereinafter, also referred to as “HDI”), 1, 6-diisocyanato-2,2,4-trimethylhexane, methyl 2,6-diisocyanatohexanoate (lysine diisocyanate) and the like. The alicyclic diisocyanate is not particularly limited. For example, 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane (isophorone diisocyanate), 1,3-bis (isocyanatomethyl) cyclohexane (water Hydrogenated diphenylmethane diisocyanate), bis (4-isocyanatocyclohexyl) methane (hydrogenated diphenylmethane diisocyanate), 1,4-diisocyanatocyclohexane, and the like. Among them, HDI, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are preferable because they are easily available industrially. Among them, HDI is more preferable because the balance between the weather resistance and the flexibility of the coating film is very excellent. Hereinafter, the aliphatic diisocyanate and the alicyclic diisocyanate are collectively referred to as diisocyanate.

  In the present embodiment, the “polyisocyanate resin” refers to a resin whose gel fraction is measured and whose weight residual ratio is 45% or more. In this embodiment, about 0.1 g of the sample is immersed in acetone at 20 ° C. for 24 hours, and after the sample is taken out, the weight of the product dried at 105 ° C. for 1 hour is measured. Ask for.

  The polyisocyanate resin used in the present embodiment preferably contains an allophanate group. In the polyisocyanate resin used in the present embodiment, the molar ratio between the isocyanurate group and the allophanate group (isocyanurate group / allophanate group) is preferably in the range of 99/1 to 50/50. The polyisocyanate resin used in the present embodiment has better flexibility if the molar ratio between the isocyanurate group and the allophane group (isocyanurate group / allophanate group) is 99/1 or less, and may be 50/50 or more. If it is, the heat resistance becomes better. In the polyisocyanate resin used in the present embodiment, the molar ratio between the isocyanurate group and the allophanate group (isocyanurate group / allophanate group) is more preferably 99/1 to 60/40 from the viewpoint of obtaining better heat resistance. , More preferably 99/1 to 70/30, still more preferably 99/1 to 80/20, and particularly preferably 98/2 to 90/10. The molar ratio between the isocyanurate and allophanate groups in the polyisocyanate resin can be measured by freeze-pulverizing the polyisocyanate resin and using 13C-NMR. Can be measured.

  In the polyisocyanate resin used in the present embodiment, the molar ratio of the isocyanurate group to the total of the urethane group and the urea group (isocyanurate group / (urethane group + urea group)) is in the range of 100/0 to 95/5. It is preferred that When the isocyanurate group / (urethane group + urea group) is in the range of 100/0 to 95/5, better heat resistance can be obtained. In the polyisocyanate resin used in the present embodiment, the ratio of isocyanurate group / (urethane group + urea group) is more preferably 100/0 to 96/4, and further preferably 100/0 to 97/3. In this embodiment, the isocyanurate group / (urethane group + urea group) can be measured by the ATR method of FT-IR, and can be measured in detail by the method described in Examples described later. .

  The polyisocyanate resin used in the present embodiment has a characteristic that heat resistance is good. The heat resistance of the polyisocyanate resin used in the present embodiment is evaluated by, for example, a 1% weight loss temperature (hereinafter also referred to as “Td1”) and a 5% weight loss temperature (hereinafter also referred to as “Td5”).

  The polyisocyanate resin used in the present embodiment preferably has Td1 of 200 ° C. or higher, more preferably 230 ° C. or higher, and still more preferably 250 ° C. or higher. The upper limit of Td1 is not particularly limited, but is, for example, 600 ° C. or less.

  Further, the polyisocyanate resin used in the present embodiment preferably has Td5 of 260 ° C. or higher, more preferably 310 ° C. or higher, and still more preferably 360 ° C. or higher. The upper limit of Td5 is not particularly limited, but is, for example, 700 ° C. or less.

  The polyisocyanate resin having heat resistance as described above is, for example, a polyisocyanate composition containing a compound obtained by isocyanurating at least one type of diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates. Under a solvent-free condition until the isocyanate group (NCO group) disappearance rate becomes 90% or more.

  The fiber reinforced composite material of the present embodiment has heat resistance by including the above-mentioned polyisocyanate resin as a matrix resin.

  In the present embodiment, Td1 and Td5 can be measured by a method described in Examples described later.

The polyisocyanate resin used in the present embodiment has good water vapor transmission resistance. The water vapor permeability can be measured based on JIS Z0208. When the polyisocyanate resin used in the present embodiment has a thickness of 0.2 mm and is allowed to stand for 24 hours under conditions of a temperature of 40 ° C. and a humidity of 90 RH%, the water vapor permeability is 0.01 to 40 g / m ^2. Is preferred. When the water vapor transmission rate is 40 g / m ² or less, the water vapor transmission resistance is good. The water vapor permeability of the polyisocyanate resin used in the present embodiment is preferably 35 g / m ² or less, more preferably 30 g / m ² or less, and even more preferably 25 g / m ² or less.

  In the fiber-reinforced composite material of the present embodiment, the content of the polyisocyanate resin is preferably from 10 to 90% by mass, and more preferably from 20 to 80% by mass. When the content of the polyisocyanate resin is within the above range, the fiber reinforced composite material of the present embodiment tends to be tough and have improved heat resistance.

<< Production method of polyisocyanate resin >>
Next, a method for producing the polyisocyanate resin used in the present embodiment will be described.

  The polyisocyanate resin used in the present embodiment can be produced by using (a) a polyisocyanate composition and (b) an isocyanuration catalyst as raw materials. That is, the polyisocyanate resin used in the present embodiment is produced by subjecting the (a) polyisocyanate composition to an isocyanurate-forming reaction with an isocyanurate-forming catalyst.

The method for producing the polyisocyanate resin used in the present embodiment is not particularly limited,
(A) a polyisocyanate obtained from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates and containing an isocyanurate group, and at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates A polyisocyanate composition obtained from one kind of diisocyanate and comprising a polyisocyanate containing an allophanate group;
(B) an isocyanuration catalyst;
Using as a raw material,
It is preferable to have a step of performing an isocyanurate-forming reaction until the disappearance rate of the isocyanate group (NCO group) in the polyisocyanate composition becomes 90% or more under the condition that substantially contains no solvent.

  The (a) polyisocyanate composition used as a raw material is obtained from at least one type of diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and comprises a polyisocyanate containing an isocyanurate group, an aliphatic diisocyanate and an alicyclic ring. It is preferably obtained from at least one type of diisocyanate selected from the group consisting of formula diisocyanates, and contains a polyisocyanate containing an allophanate group.

  Even if the polyisocyanate composition contains a polyisocyanate containing an isocyanurate group and an allophanate group in one molecule, a polyisocyanate containing only an isocyanurate group in one molecule, and one molecule It may contain a polyisocyanate containing only allophanate groups.

  The isocyanurate group is composed of three molecules of a diisocyanate monomer and is represented by the following formula (1).

  The allophanate group is formed from a hydroxyl group of an alcohol and an isocyanate group, and is represented by the following formula (2).

  When a polyisocyanate containing an isocyanurate group, a polyisocyanate containing an allophanate group, or a polyisocyanate containing an isocyanurate group and an allophanate group is derived from a diisocyanate monomer, the reaction is performed using a urethanation, isocyanuration, and allophanation catalyst Is preferred. As a specific urethanization, isocyanuration and allophanation catalyst, for example, a catalyst having basicity is generally preferable, and 1) a quaternary organic ammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium and trimethylbenzylammonium is preferable. Hydroxide or an organic weak acid salt such as acetic acid or capric acid; 2) a hydroxyalkylammonium hydroxide such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium or triethylhydroxyethylammonium; Organic weak acid salts such as capric acid, 3) acetic acid, caproic acid, octylic acid, alkylcarboxylic acids such as myristic acid, for example, tin, Metal salts such as lead, lead, sodium and potassium; 4) metal alcoholates such as sodium and potassium; 5) compounds containing aminosilyl groups such as hexamethyldisilazane; 6) Mannich bases; and 7) tertiary amines. And epoxy compounds. Preferably, 1), 2) and 3) above. Aminosilyl group-containing compounds may cause side reactions such as uretdione formation depending on the conditions of use. Further preferred is 1), more preferred is an organic weak acid salt such as acetic acid or capric acid of tetraalkylammonium, and particularly preferred is caprate of tetramethylammonium.

  The polyisocyanate in the (a) polyisocyanate composition used in the present embodiment preferably contains an isocyanurate group and an allophanate group. In this case, (a) the molar ratio of the isocyanurate group to the allophanate group in the polyisocyanate in the polyisocyanate composition (hereinafter, also referred to as “molar ratio of isocyanurate group / allophanate group”) is 99/1 to 30. / 70, more preferably 98/2 to 40/60, and even more preferably 97/3 to 50/50. (A) When the molar ratio of isocyanurate group / allophanate group in the polyisocyanate in the polyisocyanate composition is in the range of 99/1 to 30/70, the resulting polyisocyanate resin has heat resistance, heat yellowing resistance, and base. Has good adhesion. The molar ratio of isocyanurate group / allophanate group in the polyisocyanate in the polyisocyanate composition (a) can be determined by 1H-NMR. In detail, it can be measured by the method described in Examples described later.

  The (a) polyisocyanate composition used in the present embodiment is preferably a polyisocyanate composition obtained using an alcohol as one of the raw materials. As the alcohol, it is preferable to use at least one selected from the group consisting of monoalcohols, dialcohols and trivalent or higher alcohols. Among them, (a) the monoalcohol is more preferable because the viscosity of the polyisocyanate composition becomes low. The monoalcohols may be used alone or in combination of two or more. In this embodiment, the carbon number of the monoalcohol is not particularly limited, but the lower limit of the carbon number of the monoalcohol is preferably 3, more preferably 4, and still more preferably 6. The upper limit of the carbon number of the monoalcohol is preferably 16, more preferably 13, and still more preferably 9. When the carbon number of the monoalcohol is 3 or more, the adhesion of the polyisocyanate resin to the reinforcing fiber becomes better, and when the carbon number of the monoalcohol is 16 or less, the water vapor permeability and gas barrier properties of the polyisocyanate resin are reduced. It will be better.

  The monoalcohol used in the present embodiment is an alcohol having an ether group in the molecule, for example, 1-butoxyethanol, 2-butoxyethanol, 1-butoxypropanol, 2-butoxypropanol, 3-butoxypropanol, ethylene glycol monobutyl ether, Propylene glycol monomethyl ether and the like, alcohols having an ester group, alcohols having a carbonyl group, alcohols having a phenyl group, for example, benzyl alcohol and the like may be contained, but a monoalcohol consisting only of a saturated hydrocarbon group is preferable. . Further, a monoalcohol having a branch is more preferable. Such a monoalcohol is not particularly limited, but for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, isoamyl alcohol , 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1-hexanol, tridecanol, pentadecanol, palmityl alcohol, stearyl alcohol, Examples thereof include cyclopentanol, cyclohexanol, methylcyclohexanol, and trimethylcyclohexanol. Among them, 1-propanol, 2-propanol, isobutanol, n-butanol, isoamyl alcohol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl- 1-hexanol, tridecanol, pentadecanol, palmityl alcohol, stearyl alcohol, and 1,3,5-trimethylcyclohexanol are the adhesiveness of the polyisocyanate resin to the reinforcing fiber, the water vapor transmission resistance, and the corrosion of the fiber-reinforced composite material. It is more preferable because it has good anti-permeability property. Isobutanol, 1-butanol, isoamyl alcohol, pentanol, 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 3,3,5-trimethyl-1 -Hexanol and tridecanol have lower viscosities and are even more preferred. 2-hexanol, 2-octanol, 2-ethyl-1-hexanol, and 3,3,5-trimethyl-1-hexanol are very excellent in compatibility with various additives and are particularly preferable.

The (a) polyisocyanate composition used in the present embodiment may contain a uretdione compound. The uretdione body has an effect of lowering the viscosity, but if it is too much, when it is taken into the polyisocyanate resin, it may be decomposed at a high temperature and deteriorate the performance of the polyisocyanate resin. In the polyisocyanate composition (a) used in the present embodiment, the content of the uretdione compound is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. The content of the uretdione compound can be measured by measuring the ratio of the area of a peak having a molecular weight of about 336 in gel permeation chromatography (hereinafter, GPC) with a differential refractometer. When there is a peak near the peak of about 336 that may interfere with the measurement, the height of the peak of the uretdione group of about 1770 cm ^{−1 is} measured using a Fourier transform infrared spectrophotometer (hereinafter, FT-IR); The ratio to the peak height of the allophanate group of about 1720 cm ^-1 can also be determined by a method of quantification using an internal standard. Hereinafter, the measurement method of GPC will be described. The measured values relating to the molecular weight of the polyisocyanate compound were all measured by the following measuring methods. Used equipment: HLC-8120 (manufactured by Tosoh Corporation), used column: TSK GEL SuperH1000, TSK GEL SuperH2000, TSK GEL SuperH3000 (all manufactured by Tosoh Corporation), sample concentration: 5 wt / vol% (for example, 1 ml of 50 mg of sample is 1 ml) Dissolved in THF), carrier: THF, detection method: differential refractometer, outflow 0.6 ml / min. , Column temperature 30 ° C). The calibration curve of GPC is polystyrene with a molecular weight of 50,000 to 2050 (PS Science Co., Ltd. PSS-06 (Mw50000), BK13007 (Mp = 20,000, Mw / Mn = 1.03), PSS-08 (Mw = 9000), PSS -09 (Mw = 4000), 5040-35125 (Mp = 2050, Mw / Mn = 1.05) and an isocyanurate of a hexamethylene diisocyanate-based polyisocyanate composition (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Corporation) (Molecular weight of trimer of isocyanurate = 504, Molecular weight of pentamer of isocyanurate = 840, Molecular weight of heptamer of isocyanurate = 1176) and HDI (Molecular weight = 168) are prepared as standard.

  The (a) polyisocyanate composition used in the present embodiment may include a urethane body. The urethane body improves the adhesion to the base material, but too much deteriorates the heat resistance of the polyisocyanate resin. In the polyisocyanate composition (a) used in the present embodiment, the content of the urethane body is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. The content of the urethane body can be determined using 1H-NMR. The total number of moles of the allophanate group and the isocyanurate group was measured by the above-mentioned method, and the hydrogen atom bonded to the nitrogen of the urethane group at about 4 to 5 ppm (1 mol of hydrogen atom per 1 mol of urethane group) By measuring the number of moles of the urethane group from the signal area of the above, the content of the urethane compound can be measured.

  (A) When producing a polyisocyanate composition, it is preferable to simultaneously carry out a urethanization reaction, an allophanation reaction and an isocyanuration reaction between an alcohol and a diisocyanate. Depending on the case, urethanization, allophanation, and isocyanuration may be performed separately. After the urethanization, the allophanation and the isocyanuration may be performed simultaneously.

  The amount of the urethanization, isocyanuration, and allophanation catalyst used is preferably 0.001 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total mass of the reaction solution. When the amount of the urethanization, isocyanuration, and allophanation catalyst is 0.001% by mass or more, the effect of the catalyst can be sufficiently exhibited. When the amount of the urethanization, isocyanuration, and allophanation catalyst is 2% by mass or less, the reaction can be easily controlled.

  (A) In producing the polyisocyanate composition, the method of adding the urethanization, isocyanuration, and allophanation catalysts is not limited. As a method of the addition, a method of adding a required amount of the allophanate-forming catalyst at a time or a method of adding the catalyst all at once may be used. Alternatively, a method of continuously adding at a constant addition rate can also be adopted.

  (A) When producing a polyisocyanate composition, the urethanization, isocyanuration, and allophanation reactions preferably proceed in the absence of a solvent, but if necessary, besides a low-polarity organic solvent described later, acetic acid Ethyl solvents such as ethyl and butyl acetate, ketone solvents such as methyl ethyl ketone, aromatic solvents such as toluene, xylene and diethylbenzene, organic solvents having no reactivity with isocyanate groups such as dialkyl polyalkylene glycol ethers, And mixtures thereof can be used as solvents.

  In this embodiment, the process of urethanization, isocyanuration, and allophanation can be traced by measuring the NCO group content of the reaction solution or by measuring the refractive index.

  The urethanization, isocyanuration and allophanation reactions can be stopped by cooling to room temperature or by adding a reaction terminator, but when using a catalyst, adding a reaction terminator suppresses side reactions. Is preferred because The addition amount of the reaction terminator is preferably 0.25 to 20 times, more preferably 0.5 to 16 times, and still more preferably 1.0 to 12 times the molar amount of the catalyst. Quantity. When the addition amount of the reaction terminator is 0.25 times or more of the catalyst, the catalyst can be completely deactivated. When the amount of the reaction terminator added is 20 times or less of the catalyst, the storage stability becomes good. Any reaction terminator may be used as long as it deactivates the catalyst. Examples of the reaction terminator include, but are not particularly limited to, for example, phosphoric acid, compounds exhibiting phosphoric acid properties such as pyrophosphoric acid, phosphoric acid, monoalkyl or dialkyl esters such as pyrophosphoric acid, halogenated acetic acid such as monochloroacetic acid, Examples include benzoyl chloride, sulfonic acid ester, sulfuric acid, sulfuric acid ester, ion exchange resin, chelating agent and the like. From an industrial point of view, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, and monoalkyl phosphates and dialkyl phosphates are preferable because they hardly corrode stainless steel. Although it does not specifically limit as a phosphoric acid monoester or a phosphoric acid diester, For example, phosphoric acid monoethyl ester, a phosphoric acid diethyl ester, a phosphoric acid monobutyl ester, a phosphoric acid dibutyl ester, a phosphoric acid mono (2-ethylhexyl) ester Or di (2-ethylhexyl) phosphate, monodecyl phosphate, didecyl phosphate, monolauryl phosphate, dilauryl phosphate, monotridecyl phosphate, ditridecyl phosphate, phosphorus Examples thereof include acid monooleyl ester, dioleyl phosphate and the like, and mixtures thereof.

  It is also preferable to stop the reaction using an adsorbent, or to stop the reaction by combining the adsorbent with the above-mentioned reaction terminator. Examples of the adsorbent include, but are not limited to, silica gel and activated carbon. The amount of the adsorbent added is preferably 1.4 to 3000 times the mass of the catalyst, more preferably 7.0 to 1500 times the mass, and still more preferably 10.0 to 700 times the mass of the catalyst. It is. If the amount of the adsorbent is at least 1.4 times the amount of the catalyst, the catalyst remaining in the polyisocyanate composition, the heat-inactivated catalyst, the reaction product of the reaction terminator and the catalyst, and the unreacted reaction terminator If the adsorbent has sufficient ability to adsorb the adsorbent and the amount of the adsorbent is 3000 times or less of the catalyst, the adsorbent can be easily removed from the polyisocyanate composition.

  After completion of the reaction, unreacted diisocyanate and solvent may be separated from the obtained polyisocyanate composition. In consideration of safety, it is preferable that unreacted diisocyanate is separated. The method for separating unreacted diisocyanate and the solvent is not particularly limited, and examples thereof include a thin film distillation method and a solvent extraction method.

  The NCO group content in the polyisocyanate in the (a) polyisocyanate composition used in the present embodiment is preferably from 5.0 to 25.0% by mass without containing a solvent or diisocyanate. (A) The lower limit of the NCO group content in the polyisocyanate in the polyisocyanate composition is more preferably 7.0% by mass, and even more preferably 10.0% by mass. (A) The upper limit of the NCO group content in the polyisocyanate in the polyisocyanate composition is preferably 24.0% by mass, and more preferably 23.0% by mass. (A) If the NCO group content in the polyisocyanate in the polyisocyanate composition is in the range of 5.0 to 25.0% by mass, the polyisocyanate composition has a low viscosity and has good compatibility with various additives. And a polyisocyanate resin having sufficient heat resistance and heat yellowing resistance can be obtained.

  In the present embodiment, the “state not containing a solvent or diisocyanate” refers to a state in which the content of the solvent and / or diisocyanate is less than 1% by mass.

  The viscosity at 25 ° C. of the (a) polyisocyanate composition used in the present embodiment is preferably 100 to 20,000 mPa.s without containing a solvent or diisocyanate. s. The lower limit of the viscosity is more preferably 150 mPa. s. The upper limit of the viscosity is more preferably 10,000 mPa.s. s. The viscosity is 100 mPa. If it is at least s, a polyisocyanate resin having sufficient crosslinkability can be obtained. When the viscosity is 20000 mPa. If it is not more than s, a polyisocyanate resin having good compatibility with various additives can be obtained.

  The number average functional group number of the NCO group in the polyisocyanate in the polyisocyanate composition (a) used in the present embodiment is preferably 2.1 or more, more preferably 2.2 or more, and still more preferably 2.4 or more. (A) When the number average functional group number of the NCO group in the polyisocyanate in the polyisocyanate composition is 2.1 or more, the polyisocyanate resin has a higher crosslinking density and is more tough. (A) The upper limit of the number average functional group number of NCO groups in the polyisocyanate in the polyisocyanate composition is not particularly limited, but is, for example, 8.0 or less.

  The (a) polyisocyanate composition used in the present embodiment can be used even when mixed with an organic solvent. The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ester solvents, ether solvents, and low-polar organic solvents. These can be used alone or as a mixture. The low-polarity organic solvent is an organic solvent containing an aliphatic or alicyclic hydrocarbon-based solvent as a main component, but contains a small amount of an aromatic hydrocarbon-based solvent, an ester-based solvent, an ether-based solvent, or the like. It may be.

  As the (b) isocyanuration catalyst used in the present embodiment, the above-described urethanization, isocyanuration, and allophanation catalysts can be used. As a specific urethanization, isocyanuration and allophanation catalyst, for example, a catalyst having basicity is generally preferable, and 1) a quaternary organic ammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium and trimethylbenzylammonium is preferable. Hydroxide or an organic weak acid salt such as acetic acid or capric acid; 2) a hydroxyalkylammonium hydroxide such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium or triethylhydroxyethylammonium; Organic weak acid salts such as capric acid, 3) acetic acid, caproic acid, octylic acid, alkylcarboxylic acids such as myristic acid, for example, tin, Metal salts such as lead, lead, sodium and potassium; 4) metal alcoholates such as sodium and potassium; 5) compounds containing aminosilyl groups such as hexamethyldisilazane; 6) Mannich bases; and 7) tertiary amines. And epoxy compounds. Preferably, 1), 2) and 3) above. Aminosilyl group-containing compounds may cause side reactions such as uretdione formation depending on the conditions of use. More preferably, it is a quaternary organic ammonium salt of 1), further preferably, an organic weak acid salt such as acetic acid or capric acid of tetraalkylammonium, and particularly preferably a caprate of tetramethylammonium.

  The amount of the (b) isocyanuration catalyst to be added is preferably in the range of 100 to 10,000 ppm based on the solid content of the (a) polyisocyanate composition. If the amount of the (b) isocyanurate-forming catalyst is 100 ppm or more, the reactivity is sufficient. If the amount of the (b) isocyanurate-forming catalyst is 10,000 ppm or less, the physical properties of the polyisocyanate resin are not affected. . (B) The lower limit of the amount of the isocyanurate-forming catalyst added is more preferably 500 ppm or more, further preferably 1000 ppm or more, and particularly preferably 1500 ppm or more. (B) The upper limit of the amount of the isocyanuration catalyst to be added is more preferably 5000 ppm or less, and further preferably 3000 ppm or less.

  The reaction temperature at the time of producing the polyisocyanate resin used in the present embodiment is not particularly limited, but is preferably from 60 to 300 ° C. from the viewpoint of curability and color tone. If the reaction temperature is 60 ° C. or higher, there is no problem in the curability of the polyisocyanate resin, and if the reaction temperature is 300 ° C. or lower, the color tone, particularly yellowness, of the polyisocyanate resin decreases. The reaction temperature is more preferably from 80 to 270 ° C, even more preferably from 100 to 250 ° C.

  (B) A diluent can be used as needed for the isocyanuration catalyst. As the diluent, those which react with NCO groups in the polyisocyanate in the polyisocyanate composition and are taken into the system can be used. Although not particularly limited, for example, a compound having an active hydrogen group can be used as a diluent, and among them, an alcohol solvent is preferable because the viscosity is reduced and the dispersibility of the catalyst is improved. These diluents can be used alone or in combination of two or more.

  In the method for producing a polyisocyanate resin used in the present embodiment, the step of performing the above-mentioned isocyanuration reaction is performed under a condition that does not substantially contain a solvent. The condition that substantially does not contain a solvent means a condition in which the solvent is 5% by mass or less based on the polyisocyanate composition (a). (A) If the amount of the solvent is 5% by mass or less based on the polyisocyanate composition, the effect of the weight reduction of the polyisocyanate resin can be ignored. Preferably, the solvent is at most 3% by mass, more preferably at most 1% by mass, based on the polyisocyanate composition (a).

  In the method for producing a polyisocyanate resin used in the present embodiment, in the step of performing the above isocyanuration reaction, (a) the isocyanuration reaction is performed until the disappearance rate of the isocyanate group in the polyisocyanate composition becomes 90% or more. (A) When the disappearance rate of the isocyanate group in the polyisocyanate composition is 90% or more, the heat resistance and the like of the polyisocyanate resin are sufficient. (A) The rate of disappearance of isocyanate groups in the polyisocyanate composition is more preferably 91% or more, and still more preferably 92% or more.

  In the method for producing a polyisocyanate resin used in the present embodiment, (c) an antioxidant can be further used as a raw material. The (c) antioxidant may be added at the stage of producing the polyisocyanate resin, or may be added in advance to the (a) polyisocyanate composition. Further, (c) the antioxidant may be used in combination of two or more kinds.

  (C) The antioxidant is not particularly limited, and examples thereof include a light stabilizer and a heat stabilizer.

  The light stabilizer is not particularly limited, and examples thereof include hindered amine light stabilizers, benzophenone light stabilizers, benzotriazole light stabilizers, triazine light stabilizers, and cyanoacrylate light stabilizers. The hindered amine-based light stabilizer is not particularly limited. For example, ADK STAB LA-52, ADK STAB LA-68, ADK STAB LA-77Y (trade name, manufactured by ADK), Tinuvin 622, Tinuvin 765, Tinuvin 770, Tinuvin 791 (Trade name, manufactured by BASF). The benzophenone-based light stabilizer is not particularly limited, and examples thereof include Chimassorb 81 (trade name, manufactured by BASF). The benzotriazole-based light stabilizer is not particularly limited, and examples thereof include Tinuvin P and Tinuvin 234 (trade name, manufactured by BASF). The triazine-based light stabilizer is not particularly limited, and examples thereof include Tinuvin 1577ED (trade name, manufactured by BASF). The cyanoacrylate-based light stabilizer is not particularly limited, and examples thereof include Uvinul 3035 (trade name, manufactured by BASF).

  Examples of the heat stabilizer include, but are not particularly limited to, hindered phenol-based heat stabilizer, phosphorus-containing heat stabilizer, sulfur-containing heat stabilizer, vitamin E-based heat stabilizer, hydroxyamine-based heat stabilizer, and the like. No. Examples of the hindered phenol-based heat stabilizer include, but are not particularly limited to, dibutylhydroxytoluene (hereinafter, BHT), Irganox 1010, Irganox 1135, Irganox 1330, Irganox 3114, Irganox 565, Irganox 5057, Irganox 1520L (trade name, manufactured by BASF), Adekastab AO-20, Adekastab AO-30, Adekastab AO-50, Adekastab AO-60, Adekastab AO-80 (trade name, manufactured by Adeka Corporation) and the like. The phosphorus-containing heat stabilizer is not particularly limited. For example, Irgafos 168, Irgafos 38 (trade name, manufactured by BASF), Adekastab PEP-8, Adekastab HP-10, Adekastab 1178, Adekastab C (trade name, stock Adeka Co., Ltd.) and Sumilizer GP (trade name, manufactured by Sumitomo Chemical Co., Ltd.). The sulfur-containing heat stabilizer is not particularly limited, and includes, for example, Irganox PS800FL (trade name, manufactured by BASF). The vitamin E-based heat stabilizer is not particularly limited, and includes, for example, Irganox E201 (trade name, manufactured by BASF). Examples of the hydroxyamine-based heat stabilizer include, but are not particularly limited to, Irgas Tab FS042 (trade name, manufactured by BASF) and the like.

  In the method for producing a polyisocyanate resin used in the present embodiment, suitable antioxidants include a hindered phenol antioxidant, a hindered amine antioxidant, a sulfur-containing antioxidant, and a phosphorus-containing antioxidant. It is at least one selected from the group. More preferred antioxidants are Tinuvin 765, BHT, Irganox 565, Irganox 5057, Adekastab C, and Sumilizer GP. Among them, BHT, Sumilizer GP, and Irganox 5057 are more preferable because they are effective when added in small amounts.

  The method for producing the polyisocyanate resin used in the present embodiment, depending on the purpose and application, within a range that does not impair the effects of the present invention, a curing accelerator as a promoter, a silane coupling agent for improving adhesion, Various additives such as a coating film surface hydrophilizing agent, a catalyst, a leveling agent, a plasticizer, a surfactant, a coloring pigment, and a dye can also be used as a mixture. These additives may be added at the stage of producing the polyisocyanate resin, or may be added in advance to (a) the polyisocyanate composition. These additives may be used in combination of two or more.

  Examples of the curing accelerator as a promoter include, but are not particularly limited to, for example, dibutyltin dilaurate, dioctyltin dilaurate, dialkyltin dicarboxylates such as dibutyltin diacetate, tin oxide compounds such as dibutyltin oxide, and 2-ethylhexane. Metal carboxylate such as tin oxalate, zinc 2-ethylhexanoate, cobalt salt, etc., triethylamine, pyridine, methylpyridine, benzyldimethylamine, N, N-dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N, N Tertiary amines such as' -endoethylenepiperazine and N, N'-dimethylpiperazine, and the like.

≪Reinforced fiber≫
The reinforcing fibers used in the present embodiment are not particularly limited, and known ones can be used. Examples include carbon fiber, graphite fiber, silicon carbide fiber, alumina fiber, glass fiber, aramid fiber, polyamide fiber, polyester fiber, polyurethane fiber, polyethylene fiber, cellulose fiber, and the like. Among them, as the reinforcing fibers used in the present embodiment, carbon fibers and cellulose fibers are preferable, and carbon fibers are more preferable, from the viewpoint of compatibility with the above-mentioned polyisocyanate resin. When such a reinforcing fiber is used, the compatibility with the above-described polyisocyanate resin is improved, and the heat resistance and the corrosive gas permeation prevention of the fiber reinforced composite material are further improved. These can be used in combination of two or more. Further, it can be used in combination with a known filler. For example, calcium carbonate, silica, clay, titanium oxide, glass beads, graphite, carbon black and the like.

  In the fiber-reinforced composite material of the present embodiment, the content of the reinforcing fibers is preferably from 10 to 90% by mass, and more preferably from 20 to 80% by mass. When the content of the reinforcing fiber is within the above range, the fiber reinforced composite material of the present embodiment tends to have excellent durability.

製造 Manufacturing method of fiber reinforced composite material≫
The method for producing the fiber-reinforced composite material of the present embodiment is not particularly limited, and includes, for example, a method of impregnating the above-mentioned polyisocyanate resin into the reinforcing fibers.

≪Application≫
The fiber reinforced composite material of the present embodiment includes a polyisocyanate resin having both heat resistance and impact resistance, and further having good water vapor transmission resistance. Therefore, the fiber-reinforced composite material of the present embodiment is suitable for a material member for applications such as automobiles, aircraft, and windmill blades.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.

  Each measuring method in this example was as follows.

<NCO group content>
The isocyanate group (NCO group) content in the polyisocyanate in the polyisocyanate composition is determined by reacting the isocyanate group in the polyisocyanate in the polyisocyanate composition with an excess of 2N amine (a toluene solution of di-n-butylamine). The obtained reaction solution was determined by back titration with 1N hydrochloric acid.

<Viscosity>
The viscosity was measured at 25 ° C. using an E-type viscometer (Tokimec Co., Ltd.).

  In the measurement, a standard rotor (1 ° 34 ′ × R24) was used, and the rotation speed of the standard rotor was as follows.

100r. p. m. (When the viscosity is less than 128 mPa.s)
50r. p. m. (When the viscosity is 128 mPa.s or more and less than 256 mPa.s)
20r. p. m. (When the viscosity is 256 mPa.s or more and less than 640 mPa.s)
10r. p. m. (When the viscosity is 640 mPa.s or more and less than 1280 mPa.s)
5r. p. m. (When the viscosity is 1280 mPa.s or more and less than 2560 mPa.s)
<Number average number of functional groups>
The number average functional group number of the isocyanate group (NCO group) in the polyisocyanate in the polyisocyanate composition was determined by the following equation.

<Molar ratio of isocyanurate group / allophanate group in polyisocyanate in polyisocyanate composition>
The molar ratio of isocyanurate group / allophanate group in the polyisocyanate in the polyisocyanate composition was determined as follows. First, the polyisocyanate composition was dissolved in deuterated chloroform at a concentration of 10% by mass (0.03% by mass of tetramethylsilane was added to the polyisocyanate composition), and the obtained solution was subjected to 1H-NMR (Bruker. BioSpin Avance 500 (manufactured by Bio Spin Co., Ltd.) was measured. As a chemical shift standard, the hydrogen signal of tetramethylsilane was set to 0 ppm. From a spectrum obtained by 1H-NMR measurement, a signal of a hydrogen atom bonded to nitrogen of the allophanate group at about 8.5 ppm (1 mol of hydrogen atom per 1 mol of allophanate group) and an isocyanurate group at about 3.85 ppm And the area of the signal of the hydrogen atom of the methylene group (6 mol of hydrogen atom per 1 mol of isocyanurate group) adjacent to was measured.

  Based on the measured values, the molar ratio of isocyanurate group / allophanate group was determined by (signal area around 3.85 ppm / 6) / (signal area around 8.5 ppm).

<Erase rate>
By the ATR method of FT-IR (FT / IR-4200 manufactured by JASCO Corporation), IR spectra of the polyisocyanate composition before the reaction and the polyisocyanate resin after the reaction were measured. Based on the measurement result, the disappearance rate of the isocyanate group (NCO group) was determined by the following equation.

NCO group peak: around 2270 cm ^-1 , CH ₂ group peak: around 2930 cm ^-1 <Molar ratio of isocyanurate group / (urethane group + urea group) in polyisocyanate resin>
The IR spectrum of the polyisocyanate resin was measured by the ATR method of FT-IR (FT / IR-4200 manufactured by JASCO Corporation). From the peak of the carbonyl group of the isocyanurate group (around 1690 cm ^-1 ) and the NH peak of the urethane group and urea group (around 3400 cm ^-1 ), the molar ratio of isocyanurate group / (urethane group + urea group) is determined. I asked.

<Mole ratio of isocyanurate group / allophanate group in polyisocyanate resin>
The molar ratio of isocyanurate group / allophanate group in the polyisocyanate resin was determined as follows. First, the polyisocyanate resin was freeze-pulverized, and 13C-NMR DD / MAS (Dipolar Decoupling / Magic Angle Spinning) (BioSpin Avance 500, manufactured by Bruker Biospin Co., Ltd.) was measured on the obtained pulverized product. From the spectrum obtained by the measurement, the carbonyl group signal area of the isocyanurate group (around 149 ppm) and the carbonyl group signal area of the allophanate group (152 to 160 ppm region) were determined. Based on the results, the molar ratio of isocyanurate group / allophanate group was determined as (signal area around 149 ppm / 3) / (signal area in 152 to 160 ppm area / 2).

<Thermogravimetric analysis>
The thermogravimetric analysis was performed using TG-DTA (TG / DTA6200 manufactured by Seiko Instruments Inc.) under the conditions of a nitrogen flow rate of 100 ml / min and a heating rate of 10 ° C./min. In addition, Td1 and Td5 indicate the 1% weight loss temperature and the 5% weight loss temperature of the measurement sample, respectively.

<Impact test>
The impact test was performed as follows using a DuPont type impact resistance tester. A 1/4 inch hammer was set on a 1 mm thick polyisocyanate resin sample, a 1000 g weight was dropped from a predetermined height, and the presence or absence of cracks in the coating film was visually checked. The maximum height (cm) at which cracking of the coating film was not observed was indicated as impact resistance.

<Water vapor permeability test>
The water vapor permeability test was performed as follows. Using a polyisocyanate resin having a thickness of 0.2 mm, the measurement was performed under condition B (temperature: 40 ° C., humidity: 90 RH%) based on JIS Z0208 (test method for moisture permeability of moisture-proof packaging material).

[Synthesis Example 1]
The inside of a four-necked flask (reactor) equipped with a stirrer, a thermometer and a condenser was purged with nitrogen, and 600 g of HDI and 10 g of isobutanol were charged into the reactor and urethanized at 90 ° C. for 1 hour. Was. Thereafter, 0.01 g of tetramethylammonium capryate was added as an isocyanurate-forming catalyst, and allophanate-formation and isocyanurate-formation reaction was performed. When the change in the refractive index of the reaction solution became 0.010, an aqueous 85% phosphoric acid solution was added. The reaction was stopped by adding 0.03 g. The reaction solution was kept at 100 ° C. for 1 hour to completely deactivate the catalyst.

  After the reaction solution was filtered, unreacted HDI was removed from the filtrate using a falling thin film distillation apparatus to obtain a polyisocyanate composition.

  The obtained polyisocyanate composition is a transparent liquid, yield 180 g, viscosity 700 mPa.s. s, the NCO group content was 21.2% by mass, and the number average number of functional groups was 2.8. When NMR was measured on the obtained polyisocyanate composition, the molar ratio of isocyanurate groups to allophanate groups (isocyanurate groups / allophanate groups) was 70/30. Let the obtained polyisocyanate composition be M-1.

[Synthesis Example 2]
The same reactor as in Synthesis Example 1 was charged with 500 g of HDI and 2 g of 2-ethyl-1-hexanol. The temperature in the reactor was increased under stirring, and when the temperature reached 70 ° C., 0.05 g of tetramethylammonium capryate was added to the reactor as an isocyanuration catalyst, and urethanation, allophanation, and isocyanuration were performed. When the change in the refractive index of the reaction solution became 0.02, 0.08 g of an 85% aqueous phosphoric acid solution was added to stop the reaction. Thereafter, the reaction solution was kept at 90 ° C. for 1 hour to completely deactivate the catalyst.

  After the reaction solution was filtered, unreacted HDI was removed from the filtrate using a falling thin film distillation apparatus to obtain a polyisocyanate composition.

  The obtained polyisocyanate composition is a transparent liquid, yield 200 g, viscosity 3000 mPa.s. s, the NCO group content was 21.5% by mass, and the number average functional group number was 3.4. The yield was 40%. When the NMR of the obtained polyisocyanate composition was measured, the molar ratio between the isocyanurate group and the allophanate group (isocyanurate group / allophanate group) was 95/5. The obtained polyisocyanate composition is designated as M-2.

[Synthesis Example 3]
The same reactor as in Synthesis Example 1 was charged with 500 g of HDI and 25 g of isopropanol, and the temperature inside the reactor was kept at 80 ° C. for 10 minutes with stirring. Thereafter, 0.01 g of tetrabutylammonium capryate was added to the reactor, and urethanation, allophanation, and isocyanuration reactions were performed. When the change in the refractive index of the reaction solution reached 0.015, phosphoric acid was added. The reaction was stopped by adding 0.02 g of a 0.1% aqueous solution. The reaction solution was kept at 80 ° C. for 1 hour to completely deactivate the catalyst.

  After the reaction solution was filtered, unreacted HDI was removed from the filtrate using a falling thin film distillation apparatus to obtain a polyisocyanate composition.

The resulting polyisocyanate composition is a transparent liquid, yield 260 g, viscosity 450 mPa.s. s, the NCO content was 19.0% by mass, and the number average number of functional groups was 2.4. The yield was 50%. When the NMR of the obtained polyisocyanate composition was measured, the molar ratio of isocyanurate group / allophanate group was 40/60. The obtained polyisocyanate composition is designated as M-3.
[Synthesis Example 4]
The same reactor as in Synthesis Example 1 was charged with 500 g of HDI and 70 g of tridecanol, and the temperature inside the reactor was kept at 80 ° C. for 10 minutes with stirring. Thereafter, 0.01 g of N, N, N-trimethyl-N-benzylammonium hydroxide is added to the reactor, and urethanation, allophanation, and isocyanuration reactions are performed. When it became 016, 0.02 g of an 85% aqueous phosphoric acid solution was added to stop the reaction. The reaction solution was kept at 80 ° C. for 1 hour to completely deactivate the catalyst.

  After the reaction solution was filtered, unreacted HDI was removed from the filtrate using a falling thin film distillation apparatus to obtain a polyisocyanate composition.

The obtained polyisocyanate composition is a transparent liquid, yield 310 g, viscosity 600 mPa.s. s, the NCO group content was 17.0% by mass, and the number average number of functional groups was 2.5. The yield was 55%. When the NMR of the obtained polyisocyanate composition was measured, the molar ratio of isocyanurate group / allophanate group was 50/50. The obtained polyisocyanate composition is designated as M-4.
[Synthesis Example 5]
A polyisocyanate composition was obtained by mixing 90 parts by mass of M-2 and 10 parts by mass of VESTANAT T1890 (an isocyanurate of IPDI manufactured by Evonik). The obtained polyisocyanate composition is a transparent liquid having a viscosity of 5000 mPa.s. s, the NCO group content was 21.2% by mass, and the number average number of functional groups was 3.3. When NMR was measured on the obtained polyisocyanate composition, the molar ratio of isocyanurate group / allophanate group was 96/4. Let the obtained polyisocyanate composition be M-5.
[Synthesis Example 6]
The same reactor as in Synthesis Example 1 was charged with 600 g of HDI and 70 g of 2-ethyl-1-hexanol, and the temperature inside the reactor was kept at 80 ° C. for 10 minutes with stirring. Thereafter, 0.01 g of tetramethylammonium capryate was added to the reactor, and urethanation, allophanation, and isocyanuration reactions were performed. When the change in the refractive index of the reaction solution reached 0.014, phosphoric acid 85 The reaction was stopped by adding 0.02 g of a 0.1% aqueous solution. The reaction solution was kept at 80 ° C. for 1 hour to completely deactivate the catalyst.

  After the reaction solution was filtered, unreacted HDI was removed from the filtrate using a falling thin film distillation apparatus to obtain a polyisocyanate composition.

The resulting polyisocyanate composition is a transparent liquid, yield 330 g, viscosity 350 mPa.s. s, the NCO group content was 17.5% by mass, and the number average number of functional groups was 2.3. The yield was 50%. When NMR was measured on the obtained polyisocyanate composition, the molar ratio of isocyanurate group / allophanate group was 30/70. The obtained polyisocyanate composition was designated as M-6 [Synthesis Example 7].
The same reactor as in Synthesis Example 1 was charged with 600 g of HDI and 20 g of 1,4-butanediol, and the temperature in the reactor was maintained at 160 ° C. for 1 hour with stirring.

  Unreacted HDI was removed from the filtrate of the reaction solution using a falling thin film distillation apparatus to obtain a polyisocyanate composition.

The obtained polyisocyanate composition is a transparent liquid, yield 110 g, viscosity 500 mPa.s. s, the NCO group content was 19.4% by mass, and the number average number of functional groups was 2.1. About the obtained polyisocyanate composition, let the obtained polyisocyanate composition be M-7.
[Synthesis Example 8]
95 parts by mass of M-2 and 5 parts by mass of M-7 were mixed to obtain a polyisocyanate composition. The obtained polyisocyanate composition is a transparent liquid having a viscosity of 2400 mPa.s. s, the NCO group content was 20.3% by mass, and the number average number of functional groups was 3.2. When NMR was measured on the obtained polyisocyanate composition, the molar ratio of isocyanurate group / allophanate group (isocyanurate group / allophanate group) was 97/3. Let the obtained polyisocyanate composition be M-8.

[Synthesis Example 9]
The same reactor as in Synthesis Example 1 was charged with 1,000 g of HDI and 80 g of hexanol, and the temperature inside the reactor was kept at 90 ° C. for 1 hour with stirring. Thereafter, the temperature in the reactor was increased to 130 ° C., and 0.1 g of zirconium 2-ethylhexanoate was added to the reactor to perform urethanization, allophanation, and isocyanuration reactions. When the change became 0.005, 4.6 g of a 10% 2-ethyl-1-hexanol solution of pyrophosphoric acid was added to stop the reaction. The reaction solution was kept at 130 ° C. for 1 hour to completely deactivate the catalyst.

  After the reaction solution was filtered, unreacted HDI was removed from the filtrate using a falling thin film distillation apparatus to obtain a polyisocyanate composition.

The obtained polyisocyanate composition is a transparent liquid, yield 270 g, viscosity 120 mPa.s. s, the NCO group content was 18.0% by mass, and the number average number of functional groups was 2.0. The yield was 25%. When NMR was measured on the obtained polyisocyanate composition, the molar ratio of isocyanurate group / allophanate group was 3/97. Let the obtained polyisocyanate composition be M-9.
[Synthesis Example 10]
20 parts by mass of M-1 and 80 parts by mass of M-9 were mixed to obtain a polyisocyanate composition. The obtained polyisocyanate composition is a transparent liquid having a viscosity of 200 mPa.s. s, the NCO group content was 21.0% by mass, and the number average number of functional groups was 3.0. When NMR was measured for the obtained polyisocyanate composition, the molar ratio of isocyanurate group / allophanate group (isocyanurate group / allophanate group) was 20/80. Let the obtained polyisocyanate composition be M-10.
[Synthesis Example 11]
The same reactor as in Synthesis Example 1 was charged with 500 g of HDI, 0.02 g of tetramethylammonium capryate was added as an isocyanuration catalyst, and allophanation and isocyanuration reactions were performed. When the pH reached 0.011, 0.06 g of an aqueous 85% phosphoric acid solution was added to stop the reaction. The reaction solution was kept at 100 ° C. for 1 hour to completely deactivate the catalyst.

  After the reaction solution was filtered, unreacted HDI was removed from the filtrate using a falling thin film distillation apparatus to obtain a polyisocyanate composition.

  The obtained polyisocyanate composition is a transparent liquid, yield 130 g, viscosity 1600 mPa.s. s, the NCO group content was 23.4% by mass, and the number average functional group number was 3.4. When NMR was measured on the obtained polyisocyanate composition, the molar ratio of isocyanurate groups to allophanate groups (isocyanurate groups / allophanate groups) was 100/0. Let the obtained polyisocyanate composition be M-11.

[Production Example 1]
20 g of M-1 as a polyisocyanate composition and 2,000 ppm of N, N, N-trimethyl-N-benzylammonium hydroxide as an isocyanuration catalyst with respect to the solid content of the polyisocyanate composition were mixed under vacuum stirring and defoaming. Using a mixer (V-mini300, manufactured by EME Co., Ltd.), the mixture was allowed to stand in a vacuum state for 5 minutes, and then stirred at 1500 rpm for 5 minutes while maintaining the vacuum to obtain a reaction solution. The obtained reaction solution was poured into a petri dish and left at 150 ° C. for 1 hour to obtain a polyisocyanate resin K-1 having a predetermined thickness. K-1 had an isocyanurate / allophanate group ratio of 80/20, Td1 of 290 ° C., and Td5 of 355 ° C.

[Production Examples 2 to 12 and Reference Production Example 1 ]
Polyisocyanate resins K-2 to K-13 were obtained in the same manner as in Production Example 1 except that the raw materials and reaction conditions were as shown in Table 1. Table 1 shows various measurement results of the obtained polyisocyanate resins K-2 to K-13.

[Comparative Production Example 1]
A polyurethane resin was prepared as follows.

  An acrylic polyol (trade name “SETALUX1767” of Nuplex Co., resin concentration 65%, hydroxyl value 150 mg / g of resin) as a main component polyol composition, and a polyisocyanate composition M-4 as a curing agent were used. Was adjusted so that the molar ratio was 1/1. As a solvent, urethane thinner (toluene (manufactured by Wako Pure Chemical Industries, Ltd.): butyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.): ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.): xylene (manufactured by Wako Pure Chemical Industries, Ltd.) ): Propylene glycol methyl ether AC (manufactured by Gordo Solvent Co., Ltd.) = 30: 30: 20: 15: 5) to adjust the solid content to 50% by mass. It was dried at 23 ° C. for 7 days and completely cured. Thereafter, the solvent was completely removed by vacuum drying at 80 ° C. for 24 hours to obtain a polyurethane resin L-1. Table 1 shows various measured values of the obtained polyurethane resin L-1.

[Comparative Production Example 2]
An epoxy resin was prepared as follows.

  60 parts by mass of bisphenol A type epoxy resin jER827 (manufactured by Mitsubishi Chemical), 40 parts by mass of jER1001 (manufactured by Mitsubishi Chemical), and 4 parts by mass of DICY-12 (manufactured by Mitsubishi Chemical) as a curing agent were added and mixed. The epoxy resin L-2 was obtained by heating at 160 degreeC for 2 hours. Table 1 shows various measured values of the obtained epoxy resin L-2.

[Examples 1 to 12 and Reference Example 1 ]
TENAX HTS40, a PAN-based carbon fiber, having a filament count of 3000 (trade name: manufactured by Toho Tenax Co., Ltd.) was used as the reinforcing fiber, and 30 parts by mass was added to 100 parts by mass of the polyisocyanate composition. After adding a predetermined amount of the additive, the mixture was left under vacuum for 5 minutes using a vacuum stirring and defoaming mixer (V-mini300 manufactured by EME Co., Ltd.), and then stirred at 1500 rpm for 5 minutes while maintaining the vacuum. Thus, a reaction solution containing a reinforcing fiber was obtained. Thereafter, the obtained reinforcing fiber-containing reaction liquid was cured on an aluminum plate to prepare a 0.2 mm-thick sample plate (fiber-reinforced composite materials N-1 to N-13). Table 2 shows the conditions.

  As an evaluation of heat resistance, the sample was left standing in an oven at 250 ° C. for 24 hours.

As an evaluation of corrosive gas permeability, the obtained sample plate was sealed in a bottle containing sulfur powder, allowed to stand at 50 ° C. for 24 hours, and the state of the aluminum plate after standing was observed. If the color was discolored, it was evaluated as x. Table 2 shows the results of the corrosive gas permeability test of the produced fiber reinforced composite material.
[Comparative Example 1]
An acrylic polyol (trade name “SETALUX1767” of Nuplex Co., resin concentration 65%, hydroxyl value 150 mg / g of resin) as a main component polyol composition, and a polyisocyanate composition M-4 as a curing agent were used. Was adjusted so that the molar ratio was 1/1. As a solvent, urethane thinner (toluene (manufactured by Wako Pure Chemical Industries, Ltd.): butyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.): ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.): xylene (manufactured by Wako Pure Chemical Industries, Ltd.) ): Propylene glycol methyl ether AC (manufactured by Gordo Solvent Co., Ltd.) = Mixed at a mass ratio of 30: 30: 20: 15: 5) to adjust the solid content to 50% by mass. Obtained. Using TENAX HTS40 filament number 3000 (trade name: manufactured by Toho Tenax Co., Ltd.), which is a PAN-based carbon fiber, as a reinforcing fiber, 30 parts by mass was added to 100 parts by mass of the solid content of the reaction solution, and the mixture was stirred and mixed well. Thus, a reaction solution containing a reinforcing fiber was obtained. Thereafter, the obtained reinforcing fiber-containing reaction liquid was applied on an aluminum plate, dried at 23 ° C. for 7 days, and completely cured. Thereafter, the solvent was completely removed by vacuum drying at 80 ° C. for 24 hours to prepare a sample plate (fiber-reinforced composite material O-1) having a thickness of 0.2 mm. The obtained fiber reinforced composite material O-1 was evaluated for heat resistance and corrosive gas permeability test in the same manner as in each of the above examples. Table 2 shows the results.
[Comparative Example 2]
60 parts by mass of bisphenol A type epoxy resin jER827 (manufactured by Mitsubishi Chemical), 40 parts by mass of jER1001 (manufactured by Mitsubishi Chemical), and 4 parts by mass of DICY-12 (manufactured by Mitsubishi Chemical) as a curing agent were added and mixed. A reaction solution was obtained. TENAX HTS40, a PAN-based carbon fiber, having a filament count of 3000 (trade name: manufactured by Toho Tenax Co., Ltd.) was used as the reinforcing fiber, and 30 parts by mass was added to 100 parts by mass of the reaction solution, and the mixture was sufficiently mixed by stirring and reinforced. A fiber-containing reaction solution was obtained. Then, the obtained reinforcing fiber-containing reaction liquid was applied on an aluminum plate, and heated at 160 ° C. for 2 hours to prepare a 0.2 mm-thick sample plate (fiber-reinforced composite material O-2). The obtained fiber-reinforced composite material O-2 was subjected to heat resistance evaluation and corrosive gas permeability test in the same manner as in each of the above Examples. Table 2 shows the results.

  The fiber-reinforced composite material of the present invention has characteristics of heat resistance and low corrosive gas permeability, so that it can be suitably used for members such as automobiles, airplanes, and windmill blades.

Claims (7)

Including reinforced fibers and matrix resin,
It said matrix resin is obtained from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and Ri polyisocyanate resins der having isocyanurate structure as a unit structure,
The fiber reinforced composite material according to the polyisocyanate resin, wherein a molar ratio of the isocyanurate group to the allophanate group (isocyanurate group / allophanate group) is 99/1 to 50/50 .   The fiber-reinforced composite material according to claim 1, wherein the reinforcing fibers are at least one selected from the group consisting of carbon fibers and cellulose fibers.   The fiber-reinforced composite according to claim 2, wherein the reinforcing fibers are carbon fibers.   In the polyisocyanate resin, a molar ratio (isocyanurate group / (urethane group + urea group)) of the isocyanurate group to the total of the urethane group and the urea group is 100/0 to 95/5. The fiber-reinforced composite material according to any one of items 3 to 5. An automotive material member using the fiber-reinforced composite material according to any one of claims 1 to 4 . An aircraft material member using the fiber-reinforced composite material according to any one of claims 1 to 4 . A material member for a wind turbine blade using the fiber-reinforced composite material according to any one of claims 1 to 4 .