CN1712482B - Binding composition and production of plant fiber plates - Google Patents
Binding composition and production of plant fiber plates Download PDFInfo
- Publication number
- CN1712482B CN1712482B CN 200410060034 CN200410060034A CN1712482B CN 1712482 B CN1712482 B CN 1712482B CN 200410060034 CN200410060034 CN 200410060034 CN 200410060034 A CN200410060034 A CN 200410060034A CN 1712482 B CN1712482 B CN 1712482B
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- Prior art keywords
- diphenylmethanediisocyanate
- quality
- glue
- maleic anhydride
- peroxidation
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Abstract
Adhesive composition of vegetable fibre board and production of vegetable fibre board are disclosed. The composition consists of (A) organic isocyanate and (B) maleate compound or double-bond aliphatic ester compound and/or (D) radical polymer initiator. It achieves better mould unloading, water-proof and mechanical performances, and good swelling capacity and water absorption.
Description
Technical field
The present invention relates to manufacture method, and the adhesive compound that uses of this fiberboard of the good and vegetable fiberboard that mechanical properties is good of release property and water tolerance.
Background technology
Sticked with glue agent and made the sheet material of wood chip or fiber bonded particle board or fiberboard etc., as suitability for industrialized production always just since furniture material, building inner decorative material, roof sheet material etc. are before and after the nineteen fifty.As making the tackiness agent that this sheet material uses, can use melamine formaldehyde resin, resol, urea-formaldehyde resin, organic multiple isocyanate etc.
Yet, when sticking with glue agent use organic multiple isocyanate as aforementioned sheet material, though have cohesive force and water tolerance not emit the advantage of deleterious formaldehyde etc. during good and hot pressing than the tackiness agent of other resin system, sheet is bonded at the shortcoming that metal hot plate, retaining plate, mould etc. are gone up, are difficult to take out goods securely when having hot pressing.
This shortcoming is by inserting the release property sheet in advance or at per pass hot pressing operation coating releasing agent to a certain degree solution can be arranged in hot plate, retaining plate, mould etc. before compacting, but impracticable because manufacturing process is complicated.
In addition, though also proposed to use hydrophilic ammonia carbamate prepolymer to make the method (opening clear 62-59004 communique with reference to Patent Document 1-spy) of multilayered particles plate, the sheet material that obtains exists water tolerance, problem that the swelling ratio when being water retting specifically is big.
In addition, the problem of release property when solving hot pressing, also proposed to use wood chip or the tackiness agent manufacturing particle board of fiber and urethane resin system or the method (opening flat 2-214602 communique) of fiberboard with reference to Patent Document 2-spy, but inadequate problem in the mechanical properties practicality of the stripping strength of the sheet material that existence obtains etc.
Summary of the invention
The object of the invention is to solve the problem of aforementioned known technology in the past, and manufacture method, and the adhesive compound that uses of this fiberboard of the good vegetable fiberboard of good and water tolerance of release property when making and mechanical properties is provided.
What the inventor concentrated on studies found that, uses with organic multiple isocyanate by the toxilic acid based compound, can solve foregoing problems, thereby has finished the present invention.
That is, the present invention is that vegetable fiberboard sticks with glue the agent composition, it is characterized in that comprising following (A) with (B),
(A) organic isocyanate,
(B) toxilic acid based compound.
The present invention is that vegetable fiberboard sticks with glue the agent composition, it is characterized in that comprising following (A), (B) with (C),
(A) organic isocyanate,
(B) toxilic acid based compound,
(C) intramolecularly has the fatty acid ester compound of two keys.
The present invention is that vegetable fiberboard sticks with glue the agent composition, it is characterized in that comprising following (A), (B) with (D),
(A) organic isocyanate,
(B) toxilic acid based compound,
(D) radical polymerization initiator.
The present invention is that vegetable fiberboard sticks with glue the agent composition, it is characterized in that comprising following (A), (B), (C) with (D).
(A) organic isocyanate
(B) toxilic acid based compound
(C) intramolecularly has the fatty acid ester compound of two keys
(D) radical polymerization initiator
In addition, the present invention is the manufacture method of vegetable fiberboard, it is characterized in that, aforesaid each vegetable fiberboard is sticked with glue the agent composition mix with sponge, and be this mixture forming tabular then, carry out radical polymerization.
Adopt the present invention, the manufacture method of good vegetable fiberboard such as the mechanical properties of the water tolerance of the good and swelling ratio of release property when making, water-intake rate etc. and stripping strength, flexural strength etc. and the adhesive compound that this fiberboard uses can be provided.
Below, the present invention is at length described.
(A) organic isocyanate as the present invention's use, for example, can enumerate 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 2,2 '-diphenylmethanediisocyanate, contain 4,4 '-diphenylmethanediisocyanate and 2,4 '-diphenylmethanediisocyanate and 2, mixture 30～70 quality % of 2 '-diphenylmethanediisocyanate and be that the diphenylmethanediisocyanate of polyphenylene polymethylene polyisocyanates (to call " aggretion type MDI " in the following text) etc. of polykaryon 70～30 quality % of main component is a polyisocyanates with three nucleomes, also can enumerate 2, the 4-tolylene diisocyanate, 2, the aromatic polyisocyanate of 6-tolylene diisocyanate and so on.Wherein, preferred diphenylmethanediisocyanate is a polyisocyanates, again, is conceived to that its steam forces down or is difficult to cause crystallization, preferred polymeric type MDI during low temperature.
In addition, also can enumerate the aromatic diisocyanate of phenylene vulcabond etc., xylylene diisocyanate, the aromatic-aliphatic vulcabond of tetramethylxylylene diisocyanate etc., tetramethylene diisocyanate, hexamethylene diisocyanate, the 3-methyl isophthalic acid, 5-pentane vulcabond, the aliphatic diisocyanate of Methionin (リ ジ Application) vulcabond etc., isophorone diisocyanate, the hydrogenation tolylene diisocyanate, the hydrogenation xylylene diisocyanate, the hydrogenation diphenylmethanediisocyanate, the alicyclic diisocyanate of hydrogenation tetramethylxylylene diisocyanate etc.
Also can use a part of modification of these isocyanate group is become biuret, allophanate, carbodiimide, uretonimine, isocyanuric acid ester (trimer), the urea diketone (modifier of dipolymer), oxazolidone, acid amides, imide etc.
In addition, also can use the modifier that these modifications is become the emulsifying water type.
These can use separately or use mixing more than 2 kinds.
As (B) toxilic acid based compound that the present invention uses, for example, can enumerate the derivative of the toxilic acid of toxilic acid, maleic anhydride etc.Wherein, preferred maleic anhydride.
These can use separately, or use mixing more than 2 kinds.
The fatty acid ester compound that two keys are arranged as (C) intramolecularly of the present invention's use; for example; can enumerate Viscotrol C and oxyalkylene affixture thereof; with the transesterify thing that with the Viscotrol C is the polyvalent alcohol of raw material; the ricinoleate of polyvalent alcohol or ricinoleic acid ester polyol; the partial dehydration thing of Viscotrol C; dehydrate; partially acylated thing or partial oxide; tung oil; soybean oil; Semen Lini oil; the oleic acid ester of polyvalent alcohol; the linoleate of polyvalent alcohol; the linolenate of polyvalent alcohol; with these is the polyvalent alcohol of main component or the ester that is called the higher unsaturated fatty acid of acryl polyvalent alcohol and so on. the glycols that also can enumerate ethylene glycol etc. is the unsaturated polyester that intramolecularly that the unsaturated polyvalent carboxylic acid condensate of the polyvalent alcohol of representative and toxilic acid or fumaric acid etc. makes has two keys; again; can enumerate vinylbenzene; Phthalic acid, diallyl ester; the example that the ethene base system monomer of Vinylstyrene etc. uses with unsaturated polyester. in addition; also can use the modifier that these modifications is become the emulsifying water type. wherein; the ester of preferred higher unsaturated fatty acid, special preferably glycerine ester.
These can use separately or use mixing more than 2 kinds.
(D) radical polymerization initiator as the present invention's use, for example, can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo, two-2-methylbutyronitrile, 2,2 '-azo-bis-iso-dimethyl, azo dicyano valeric acid, 1,1 '-azo two-(hexanaphthene-1-nitrile), 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-(4-methoxyl group-2, the 4-methyl pentane nitrile) etc. azo based compound, 1,1-two (tert-butyl hydroperoxide)-3,3, the 5-trimethyl-cyclohexane, 1,1-two (peroxidation of uncle's hexyl) hexanaphthene, 1,1-two (peroxidation of uncle's hexyl)-3,3, the 5-trimethyl-cyclohexane, 1,1-two (tert-butyl hydroperoxide) hexanaphthene, 1,1-two (tert-butyl hydroperoxide) cyclododecane, 4,4-two (tert-butyl hydroperoxide) n-butyl pentanoate, 2,2-two (tert-butyl hydroperoxide) butane, t-butyl hydroperoxide, di-isopropylbenzene hydroperoxide, hydrogen peroxide is right
Alkane, peroxidation uncle hexyl, peroxidation 1,1,3, the 3-tetramethyl butyl, the tert-butyl peroxide isopropyl benzene, dicumyl peroxide, di-t-butyl peroxide, the peroxidation isobutyryl, peroxidation 3,5, the 5-trimethyl acetyl, the peroxidation decoyl, lauroyl peroxide, stearoyl, succinic acid peroxide, benzoyl peroxide, peroxidation tolyl benzoyl, di-isopropyl peroxydicarbonate, the peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two (4-tert-butylcyclohexyl) ester, peroxy dicarbonate two-2-ethoxy ethyl ester, peroxy dicarbonate two-2-methoxyl group butyl ester, peroxy dicarbonate two-2-ethylhexyl, peroxy dicarbonate two (3-methyl-3-methoxyl group butyl) ester, α, α '-two (the new caprinoyl of peroxidation) diisopropylbenzene(DIPB), peroxidation neodecanoic acid cumyl ester, peroxidation neodecanoic acid 1,1,3,3-tetramethyl-butyl ester, peroxidation neodecanoic acid 1-cyclohexyl-1-methyl ethyl ester, peroxidation neodecanoic acid uncle polyhexamethylene, new peroxide tert-butyl caprate, the own ester of peroxidation PIVALIC ACID CRUDE (25) uncle, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, 2,5-dimethyl-2,5-two (peroxidation of 2-ethylhexyl) hexane, 1,1,3,3-tetramethyl butyl peroxidation-2-ethylhexanoate, 1-cyclohexyl-1-methylethyl peroxidation-2-ethylhexanoate, uncle's hexyl peroxidation-2-ethylhexanoate, peroxide-2-ethyl hexanoic acid tert-butyl, the peroxidation tert-butyl isobutyrate, the peroxidation lauric acid tert-butyl ester, peroxidation 3,5, the 5-tri-methyl hexanoic acid tert-butyl ester, the own ester of peroxidation sec.-propyl one carbonic acid uncle, the peroxidation sec.-propyl one carbonic acid tert-butyl ester, peroxidation-2-ethylhexyl one carbonic acid the tert-butyl ester, 2,5-dimethyl-2,5-two (benzoyl peroxidation) hexane, 2,5-dimethyl-2,5-two (toluoyl peroxidation) hexane, peroxide acetic acid butyl ester, the own ester of peroxidation phenylformic acid uncle, the m-toluyl peroxide t-butyl perbenzoate, peroxidized t-butyl perbenzoate, the organo-peroxide of m-phthalic acid two (tert-butyl hydroperoxide) ester etc.In addition, also can use the modifier that these modifications is become the emulsifying water type.
These may be used alone, can also be 2 or more kinds in combination.
In the adhesive compound of the present invention, (B) toxilic acid based compound, with respect to (A) organic isocyanate 100 mass parts, preferably use 0.01～100 mass parts, more preferred 0.1～50 mass parts, especially preferably use 0.5～20 mass parts.(C) fatty acid ester compound with respect to (A) organic isocyanate 100 mass parts, preferably uses below 500 mass parts, preferred again 10～250 mass parts, preferred especially 20～150 mass parts.(D) radical polymerization initiator with respect to (A) organic isocyanate and (B) toxilic acid based compound and (C) total amount 100 mass parts of fatty acid ester compound, preferably uses below 10 mass parts, preferably uses 0.1～5 mass parts again.
The sponge that uses as the present invention for example, can be enumerated timber (as, sal material), bark, wood fibre, rice hulls, straw (straw, rice bar, cereal bar etc.), Caulis Sacchari sinensis fiber, cork, bamboo, flax, jute (your fiber crops).Its shape is not had particular restriction, preferably use sheet.Wherein, consider from economical point, preferably straw.
These can use separately, or use mixing more than 2 kinds.
Thickness when adhesive compound of the present invention goes for forming sheet material and shape make heat fully be transmitted to inner sponge, thereby make composite material (for example OSB etc.).
The blending means of adhesive compound in sponge can according to circumstances at random be selected among the present invention, for example, (1) before use in advance with (A) organic isocyanate and (B) toxilic acid based compound with after according to circumstances with (C) fatty acid ester compound and (D) radical polymerization initiator mixes again, be blended in the sponge, perhaps (2) are with after the blending in advance of (B) toxilic acid based compound is in sponge, remix (A) organic isocyanate, and according to circumstances by order remix (C) fatty acid ester compound and (D) radical polymerization initiator arbitrarily.
In addition, (A) organic isocyanate and (B) toxilic acid based compound and (C) fatty acid ester compound that uses as required and (D) radical polymerization initiator, also can water or organic solvent diluting or disperse after spray.
In the manufacture method of vegetable fiberboard of the present invention, with respect to sponge 100 mass parts, preferred mixed glue composition 0.1～50 mass parts, preferred 0.5～25 mass parts, preferred especially 1～10 mass parts again.
Radical polymerization during vegetable fiberboard of the present invention is made, preferably by under the pressurization of hot pressing etc., heating condition, 50kg/cm for example specifically
2Below, under 100～250 ℃ the condition plate manufacturing of institute's moulding is carried out with mixture process 5～1000 seconds.
By in aforementioned pressurization, under the heating condition to plate manufacturing handle with mixture, can make moisture in (A) organic isocyanate and the straw or straw and (C) the fatty acid ester compound molecular memory hydroxyl react, (C) intramolecular pair of key generation of fatty acid ester compound radical polymerization, in addition, (B) the toxilic acid based compound reacts (Diels-Alder reaction) with (C) conjugated double bond of fatty acid ester compound, (B) toxilic acid based compound and (A) organic isocyanate reaction (maleimide formation reaction), (B) the toxilic acid based compound reacts (with the addition reaction of α-H) with (C) two keys of fatty acid ester compound, thus formation sheet material.
Description of drawings
The graphic representation of the size-grade distribution of Fig. 1 straw sheet that to be expression embodiment 1～10 use with comparative example 1～3.
Embodiment
Below, illustrate in greater detail the present invention by embodiment etc.
Embodiment 1
Straw sheet 1000g is added in the rotary blender cylinder mixture of (Japanese polyurethane industry (strain) system WC-220) 40g of the spray aggretion type MDI while rotating and maleic anhydride 0.5g.The size-grade distribution of straw sheet is shown in Fig. 1.
The straw sheet of combination treatment be filled in the wooden frame that places on the retaining plate (300 * 300 * 150mm), become homogeneous thickness, remove wooden frame after, with the pressurization hot plate at 160 ℃, 20kg/cm
2Condition under hot pressing 5 minutes, make sheet material.
The plate that the makes demoulding from the retaining plate easily.
The result who measures this plate rerum natura according to JIS A5908 is shown in table 1 with the raw material composition.
Embodiment 2
Among the embodiment 1, except replace maleic anhydride 0.5g with maleic anhydride 1.0g, other similarly make sheet material, measure rerum natura.
The sheet material that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 1.
Embodiment 3
Among the embodiment 1, except replace aggretion type MDI40g and maleic anhydride 0.5g with aggretion type MDI 30g and maleic anhydride 0.3g and Viscotrol C 30g, other similarly make sheet material, measure rerum natura.
The plate that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 1.
Embodiment 4
Among the embodiment 1, except replace aggretion type MDI 40g and maleic anhydride 0.5g with aggretion type MDI 30g and maleic anhydride 0.3g and dicumyl peroxide 0.3g, other similarly make sheet material, measure rerum natura.
The plate that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 1.
Embodiment 5
Among the embodiment 4, except replace 30g with aggretion type MDI 50g, other similarly make sheet material, measure rerum natura.
The sheet material that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 1.
Embodiment 6
Among the embodiment 4, except using Viscotrol C 30g again, other similarly make sheet material, measure rerum natura.
The sheet material that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 2.
Embodiment 7
Among the embodiment 6, except replace 0.3g with maleic anhydride 1.5g, other similarly make sheet material, measure rerum natura.
The sheet material that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 2.
Embodiment 8
Among the embodiment 6, except replace 0.3g with maleic anhydride 3.0g, other similarly make sheet material, measure rerum natura.
The sheet material that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 2.
Embodiment 9
Among the embodiment 6, except replace Viscotrol C 30g with tung oil 30g, other similarly make sheet material, measure rerum natura.
The plate that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 2.
Embodiment 10
Among the embodiment 9, except replace Viscotrol C 30g with triolein 30g, other similarly make sheet material, measure rerum natura.
The plate that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 2.
Comparative example 1
Among the embodiment 4, except not using maleic anhydride, other similarly make sheet material, measure rerum natura.
The plate that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 3.
Comparative example 2
Among the embodiment 5, except not using maleic anhydride, other similarly make sheet material, measure rerum natura.
The plate that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 3.
Comparative example 3
Among the embodiment 10, except not using maleic anhydride, other similarly make sheet material, measure rerum natura.
The plate that makes can be easily the demoulding from the retaining plate.
The rerum natura of this plate and raw material composition are shown in table 3.
Table 1
Table 2
Table 3
Claims (5)
1. vegetable fiberboard sticks with glue the agent composition, it is characterized in that, contain following (A) with (B),
(A) contain 4,4 '-diphenylmethanediisocyanate and 2,4 '-diphenylmethanediisocyanate and 2, mixture 30～70 quality % of 2 '-diphenylmethanediisocyanate and be the polyphenylene polymethylene polyisocyanates of polykaryon 70～30 quality % of main component with three nucleomes
(B) maleic anhydride.
2. vegetable fiberboard sticks with glue the agent composition, it is characterized in that containing following (A), (B) with (C),
(A) contain 4,4 '-diphenylmethanediisocyanate and 2,4 '-diphenylmethanediisocyanate and 2, mixture 30～70 quality % of 2 '-diphenylmethanediisocyanate and be the polyphenylene polymethylene polyisocyanates of polykaryon 70～30 quality % of main component with three nucleomes
(B) maleic anhydride,
(C) intramolecularly has the fatty acid ester compound of two keys.
3. vegetable fiberboard sticks with glue the agent composition, it is characterized in that, contain following (A), (B) with (D),
(A) contain 4,4 '-diphenylmethanediisocyanate and 2,4 '-diphenylmethanediisocyanate and 2, mixture 30～70 quality % of 2 '-diphenylmethanediisocyanate and be the polyphenylene polymethylene polyisocyanates of polykaryon 70～30 quality % of main component with three nucleomes
(B) maleic anhydride,
(D) radical polymerization initiator.
4. vegetable fiberboard sticks with glue the agent composition, it is characterized in that, contain following (A), (B), (C) with (D),
(A) contain 4,4 '-diphenylmethanediisocyanate and 2,4 '-diphenylmethanediisocyanate and 2, mixture 30～70 quality % of 2 '-diphenylmethanediisocyanate and be the polyphenylene polymethylene polyisocyanates of polykaryon 70～30 quality % of main component with three nucleomes
(B) maleic anhydride,
(C) intramolecularly has the fatty acid ester compound of two keys,
(D) radical polymerization initiator.
5. making the method for vegetable fiberboard, it is characterized in that, each described vegetable fiberboard of claim 1～4 is sticked with glue the agent composition mix with sponge, is the mixture forming that obtains tabular then, carries out radical polymerization.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410060034 CN1712482B (en) | 2004-06-21 | 2004-06-21 | Binding composition and production of plant fiber plates |
| JP2004291601A JP2006008971A (en) | 2004-06-21 | 2004-10-04 | Binder composition for vegetable fiber board and method for producing vegetable fiber board using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410060034 CN1712482B (en) | 2004-06-21 | 2004-06-21 | Binding composition and production of plant fiber plates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1712482A CN1712482A (en) | 2005-12-28 |
| CN1712482B true CN1712482B (en) | 2010-05-05 |
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ID=35718280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410060034 Expired - Fee Related CN1712482B (en) | 2004-06-21 | 2004-06-21 | Binding composition and production of plant fiber plates |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2006008971A (en) |
| CN (1) | CN1712482B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ612989A (en) | 2011-01-20 | 2015-01-30 | Univ Kyoto | Production method for particle board and fiber board |
| CN113103396B (en) * | 2020-01-13 | 2023-01-13 | 万华化学集团股份有限公司 | Artificial board without aldehyde addition and manufacturing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317529A (en) * | 2001-04-02 | 2001-10-17 | 广州市鹿山化工材料有限公司 | Adhesive for coating on steel pipe |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07207246A (en) * | 1994-01-19 | 1995-08-08 | Sanyo Chem Ind Ltd | Adhesive composition for laminated film |
| GB9815029D0 (en) * | 1998-07-11 | 1998-09-09 | Ici Plc | Polyisocyanate compositions |
| JP4416229B2 (en) * | 1999-11-04 | 2010-02-17 | 西松建設株式会社 | Fiberboard and method for increasing the strength of fiberboard |
| JP2001279219A (en) * | 2000-03-30 | 2001-10-10 | Nippon Polyurethane Ind Co Ltd | Adhesive composition for hot-pressed product, hot-pressed product produced by using the composition and method for producing the same |
-
2004
- 2004-06-21 CN CN 200410060034 patent/CN1712482B/en not_active Expired - Fee Related
- 2004-10-04 JP JP2004291601A patent/JP2006008971A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317529A (en) * | 2001-04-02 | 2001-10-17 | 广州市鹿山化工材料有限公司 | Adhesive for coating on steel pipe |
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| Publication number | Publication date |
|---|---|
| JP2006008971A (en) | 2006-01-12 |
| CN1712482A (en) | 2005-12-28 |
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