CN104629678B - Timber by water-fast bio-based without aldehyde adhesive and preparation method - Google Patents
Timber by water-fast bio-based without aldehyde adhesive and preparation method Download PDFInfo
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Abstract
The present invention announces a kind of water-fast bio-based of timber without aldehyde adhesive and preparation method, belongs to adhesive technical field.Without aldehyde adhesive, bio-based that this is water-fast includes that preparation method is as follows: add water in reactor containing protein material, enzyme, preservative, water resistant reinforcing modifying agent and water etc., controlling temperature is 30～55 DEG C；Be sequentially added into enzyme and soybean protein, regulate after stirring to pH value be 4～6.5, enzymolysis 20～70 minutes；Regulation pH value is 7.5～10, then is separately added into preservative and water resistant reinforcing modifying agent and stirs.The timber of the present invention is by water-fast bio-based without aldehyde adhesive environmental friendliness, excellent storage stability, and solid content is high, reduce power consumption, and bonding strength and the water resistance of adhesive are excellent, and the consumption of water resistant reinforcing modifying agent substantially reduces, and cost is remarkably decreased.
Description
Technical field
The present invention announces a kind of water-fast bio-based of timber without aldehyde adhesive and preparation method, belongs to and prepares without aldehyde adhesive
Technical field.
Background technology
Adhesive is in great demand by wood-processing industry, and the adhesive of annual consumption accounts for 60% left side of total gluing dosage
The right side, the adhesive for wood on market mainly " three-aldehyde glue " (urea-formaldehyde glue, phenol glue, carbamide glue), the most especially with
Urea-formaldehyde glue is main.Lauxite has that production technology is simple, low in raw material price, tack big, bonding strength is higher, colourless
Bright and do not pollute the feature of timber-work, its consumption once accounted for about the 80% of the total glue consumption of wood-processing industry.But use " three aldehyde
Glue " prepare plywood, produce and use during formaldehyde all can be had to release, in plywood the release phase of formaldehyde be 3～
15 years, thus cause newly-built house Indoor Air Formaldehyde to exceed standard for a long time, resident's health is caused health hazards.A lot of producers pass through
Use formaldehyde to shelter, adsorb, the means such as closing, make the burst size of formaldehyde to E2 (≤5.0mg/L), E1 (≤1.5mg/L) level
Standard or reach E0 (≤0.5mg/L) grade standard reluctantly, but when condition possesses, this part formaldehyde still can volatilize.
It addition, " Wood composite products formaldehyde standard bill " (Formaldehyde Standards for of the U.S.
Composite Wood Act) formally effective on January 3rd, 2011, the content of formaldehyde in Wood composite products is done and has strictly wanted
Ask.In order to fundamentally solve the Form aldehyde release problem of plywood, prevent the harm that residents ' health is produced, avoid above-mentioned simultaneously
The impact implementing to cause the wood gluing goods export enterprise of China of bill, exploitation has heavily without the bio-based adhesive of aldehyde
Big meaning.Become researcher research with the natural biological resource (such as protein, starch, the cellulose etc.) adhesive as raw material to open
The focus sent out, protein is processed owing to being prone to modify, is especially favored by researcher.
Patent CN200410002616.9 discloses the modifications such as sodium sulfite, villaumite, sodium lauryl sulphate, carbamide
Soybean source adhesive.Patent CN200410017054.5 disclose add the intramolecule compound that contains phenyl ring containing protein
The adhesive of raw material.Patent CN200610010370.9 discloses the Semen Glycines powder gluing that sodium hydroxide, calcium oxide, sodium silicate etc. are modified
Agent.Patent CN200710072642.2, CN200710072643.7 and CN200710072644.1 disclose tannic acid or/and boron
The Semen Glycines powder adhesive that acid is modified.But, with alkali as modifying agent, when extensin matter molecule, protein often can be hydrolyzed and break
Bad, affect the bonding strength of soybean protein adhesive and the raising of resistance to water；Non-bases modifying agent can be soybean protein
Molecular stretching and be unlikely to destroy, but the bonding strength of soybean protein adhesive and resistance to water are still difficult to reach requirement, difficult
With industrial applications.
To this end, over nearly 10 years, researcher improves the bonding strength of protein adhesive and water-fast by adding cross-linking agent
Property.
Patent CN200710164080.4 adds epoxy halides and containing 2 or above amino in Adhesive composition
Aliphatic compound or polymer.Patent CN200910072180.3 and CN200910073411.2 disclose employing dialdehyde and change
The based Wood Adhesives of property.Patent CN201010550481.5 discloses employing epoxy resin and firming agent six is hydrated triethylene diamine
Modified soy protein adhesives.Patent CN201010550477.9 discloses polyphenyl polymethylene polyisocyanates modification
Soy protein adhesives.But there is consistency problem with protein in the modifying agent of above crosslinked action, although in certain journey
Improve bonding strength and the water resistance of protein adhesive on degree, but effect is unsatisfactory, being still unable to reach industry should
Requirement.
Li etc. (Li, K et.J.Am.Oil.Chem.Soc.2004,8,487；US2006/0156954A1) high by cation
Polymers-Polyamide Polyamine Epichlorohydrin Resin (PAE), and soybean protein effect, improve to a great extent bonding strength and
Resistance to water.Patent CN201110401679.1 disclose by acid and the amine product that formed of reaction formed with anhydride reaction again water-soluble
Property firming agent, for the modification of protein adhesive.Patent CN201210393051.6 discloses by amine and bio-based binary acid
Product again with epoxy alkyl halide or 1,3-dihalo--2-propanol reaction formed water soluble polymer, for protein gluing
The modification of agent.The active reactive group of the most water-soluble cross-linked modifying agent, can be with-the COOH in protein ,-OH ,-NH2
Deng radical reaction, produce the preferable cross-linked network structure of resistance to water, and then substantially increase the water-fast of soybean protein adhesive
Property.But, the large usage quantity of above-mentioned water-soluble cross-linked modifying agent, cause the relatively costly of soybean protein adhesive；The opposing party
Face, the reactivity of above-mentioned water-soluble cross-linked modifying agent is higher, considers from product stability, and solid content is difficult to too high.
Patent CN201410305729.X utilizes the maleic anhydride compound reaction thing with polymine (PEI) as Semen sojae atricolor
The cross-linking agent of protein adhesive, action effect can compare favourably with PAE, but PEI is expensive, is unfavorable for soybean protein gluing
The industrialization of agent.
Summary of the invention
It is an object of the invention to provide a kind of water-fast bio-based of timber without aldehyde adhesive.Compared with prior art, this
Bright timber by water-fast bio-based without aldehyde adhesive with water as disperse medium, non-volatility solvent and Form aldehyde release, environmental friendliness；
The water resistant reinforcing modifying agent used in adhesive system is compared with PAE class modifying agent, and bin stability is more preferable, can carry further
The solid content of high adhesive, makes the water quantities being dried required volatilization reduce, and power consumption reduces；The bonding strength of adhesive and resistance to water
Can be the most more excellent；And the amount ratio PAE class modifying agent of water resistant reinforcing modifying agent substantially reduces, cost is notable
Decline.
To achieve these goals, present invention employs following technical scheme:
A kind of timber, includes according to mass fraction without aldehyde adhesive by water-fast bio-based:
Described is selected from soybean protein isolate, the beans defatted soy flour of protein content more than 15% or bean containing protein material
The dregs of rice, non-beans various plant defats pool (such as: degreased cottonseed meal, defat castor seed meal, the defatted peanut dregs of rice, defat rapeseed cake etc.),
The mixture of one or more in various animal proteinums (such as: gelatin, fish flour, animal osseocolla or bone meal, defat powdered egg etc.) etc.；
Wherein it is preferably soybean protein isolate, the bean cake of protein content more than 15%；The more preferably bean cake of protein content more than 20%.
Described enzyme is multiple selected from acid protease, neutral protease, alkaline protease, cellulase, hemicellulose
The mixture of one or more in synthase and amylase etc.；Wherein it is preferably acid protease, neutral protease, cellulase
With the mixture of one or more in amylase etc.；More preferably in acid protease, cellulase and amylase etc.
Kind or several mixture.The enzymolysis modified method of protein of enzyme, can avoid the chemical modifier destruction to protein,
Preferably keep the original intensity of protein and resistance to water；Can also utilize between little molecular carbon hydrate and protein simultaneously
Maillard reaction improves the resistance to water of protein adhesive product further.The method of enzyme enzymolysis, can reduce water-fast increasing
The usage amount of strong modifying agent, and then reduce product cost.
Described preservative is selected from sorbic acid, potassium sorbate, tartaric acid, plant acid, hydroxybenzoate, para hydroxybenzene first
Acetoacetic ester, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, ethoxyquin, dehydroactic acid, benzoic acid, sodium benzoate, third
Acid sodium, calcium propionate, sodium diacetate, sodium sulfite or sodium sulfite, to poly-azacyclo-quaternary ammonium salt, dodecyl dimethyl benzyl
The mixture of one or more in ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, Dodecyl trimethyl ammonium chloride etc.；
Wherein it is preferably in potassium sorbate, sodium benzoate, sodium diacetate, dodecyl dimethyl benzyl ammonium chloride, sodium sulfite etc.
The mixture of one or more；It is more preferably the one in potassium sorbate, dodecyl dimethyl benzyl ammonium chloride etc. or it mixes
Compound.
Described water resistant reinforcing modifying agent selected from polyhydric alcohol and the condensation polymer of dialdehyde, polyamide contracting urea epoxy adduct and
One in zirconium carbonate ammonium etc. or its mixture.Above-mentioned water resistant reinforcing modifying agent bin stability compared with PAE is more preferable, albumen
The solid content of matter adhesive can improve further, needs the moisture being dried to reduce during making plywood making, and then permissible
Reduce energy expenditure, play energy-conservation purpose.Above-mentioned water resistant reinforcing modifying agent is used to make bonding strength and the water resistance of adhesive
More excellent, and usage amount can substantially reduce, compared with PAE class modifying agent, the cost of adhesive is remarkably decreased.
Further, described polyhydric alcohol is selected from glycerol, trimethylolethane, tetramethylolmethane, xylitol, sorbitol, Fructus Vitis viniferae
The mixture of one or more in sugar monosaccharide and disaccharide etc.；It is preferably the one in glycerol, xylitol, sorbitol and disaccharide etc.
Or several mixture；More preferably sorbitol.Described dialdehyde is Biformyl, glutaraldehyde, hexandial and 4,4'-biphenyl two
The mixture of one or more in formaldehyde etc.；Wherein it is preferably the one in Biformyl and glutaraldehyde etc. or its mixture；More
It is preferably glutaraldehyde.
Further, described polyamide contracting urea epoxy adduct obtains through procedure below: 1) polyamine is condensed with binary acid,
2) condensation product and urea-based compound deamination, 3) deamination products and epoxy polyfunctionality compound open loop addition.
Further, described polyamine is selected from diethylenetriamine (H2NCH2CH2NHCH2CH2NH2), triethylene tetramine (H2N
CH2CH2NHCH2CH2NHCH2CH2NH2), TEPA (H2NCH2CH2NHCH2CH2NHCH2CH2NH CH2CH2NH2), spermidine
(H2N(CH2)4NH(CH2)3NH2), spermine (H2N(CH2)3NH(CH2)4NH(CH2)3NH2) etc. in the mixing of one or more
Thing, or be the mixture of above-mentioned polyamines and diamidogen, such diamidogen such as ethylenediamine (H2NCH2CH2NH2), putrescine (H2N(CH2)4NH2), cadaverine (H2N(CH2)5NH2) etc.；Wherein it is preferably in diethylenetriamine, triethylene tetramine, spermidine, spermine etc.
Kind or several mixture or its mixture with other amine above-mentioned；More preferably spermidine or its mixing with other amine above-mentioned
Thing.
Further, described binary acid is selected from malonic acid, succinic acid, adipic acid, suberic acid, SA, furan diacid, Portugal
The mixture of one or more in grape saccharic acid, tartaric acid, malic acid etc.；Wherein be preferably succinic acid, adipic acid, pungent two
The mixture of one or more in acid, furan diacid, glucaric acid etc.；More preferably adipic acid.
Further, the mixing of one or more in carbamide, biuret, acetylurea etc. of the described urea-based compound
Thing；Wherein it is preferably the one in carbamide or biuret etc. or its mixture；More preferably carbamide.
Further, described epoxy polyfunctionality compound selected from chloropropylene oxide, 1,3-dihalo--2-propanol, BDO two
Glycidyl ether, polypropylene glycol diglycidyl ether, 1,6 hexanediol diglycidylether, propanetriol-diglycidyl-ether, second two
The mixture of one or more in alcohol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether etc.；Wherein it is preferably table
Mixing of one or more in chloropharin, 1,3-dihalo--2-propanol, propanetriol-diglycidyl-ether, Ethylene glycol diglycidyl ether etc.
Compound；The more preferably one in chloropropylene oxide and Ethylene glycol diglycidyl ether etc..
Described fill material is selected from other biomass material or inorganic powder；Wherein it is preferably hydroxymethyl cellulose, hydroxyl
Sodium carboxymethylcellulose pyce, chitosan, starch, modified starch, pectin, guar gum, kieselguhr, Kaolin, Pulvis Talci, bentonite and glass
The mixture of one or more in glass silk flosssilk wadding etc.；More preferably the one in chitosan, modified starch and kieselguhr etc. or its
Mixture.
It is a further object of the present invention to provide a kind of described timber water-fast bio-based preparation method without aldehyde adhesive: will
Water adds in reactor, is warming up to 30～55 DEG C；It is sequentially added into enzyme, soybean protein and fill material, adjusts after stirring
Joint to pH value is 4～6.5, enzymolysis 20～70 minutes；Regulation pH value is 7.5～10, then is separately added into preservative and water resistant reinforcing
Modifying agent also stirs.
Due to the fact that and have employed technique scheme, have the advantages that
1) timber of the present invention by water-fast bio-based without aldehyde adhesive with water as disperse medium, non-volatility solvent and formaldehyde
Release, environmental friendliness；
2) the water resistant reinforcing modifying agent that the timber of the present invention uses without aldehyde adhesive by water-fast bio-based and PAE class modifying agent
Comparing, bin stability is more preferable, can improve the solid content of adhesive further, makes the water quantities being dried required volatilization reduce,
Plywood processing power consumption reduces；
3) timber of the present invention is excellent without bonding strength and the water resistance of aldehyde adhesive by water-fast bio-based；
4) timber of the present invention by water-fast bio-based without the amount ratio PAE class modifying agent of aldehyde adhesive water resistant reinforcing modifying agent
Substantially reducing, cost is remarkably decreased.
5) timber of the present invention is applicable to plywood, special plywood (such as: wooden by water-fast bio-based without aldehyde adhesive
Laminate, core-board etc.), density board (MDF) (such as: low density fiberboard also known as softboard, medium density fibre board (MDF) also known as
Semi-hardboard, high density fiberboard are also known as hardboard), particieboard, oriented wood chipboard (OSB), face artificial board etc.
Various wood-based plates.
Detailed description of the invention
Enzyme, preservative, the code name of fill material:
The water resistant reinforcing modifying agent that the present invention uses
Synthesis example 1 (polyhydric alcohol and the condensation polymer of dialdehyde)
The water of 80 mass parts, the sorbitol of 30 mass parts, the glutaraldehyde of 50 mass parts join in reaction bulb, are warming up to 70
DEG C, it is incubated 3h, i.e. obtains polyhydric alcohol and the condensation polymer aqueous solution of dialdehyde that active constituent content is 50%, be labeled as N-1.
Synthesis example 2 (polyamide contracting urea epoxy adduct)
The water of 5 mass parts, the spermidine of 50 mass parts, the adipic acid of 40 mass parts add in reaction bulb, are warming up to 160 DEG C
React 30 minutes, be to slowly warm up to 190 DEG C the most again, and evacuation continues reaction 2h.After breaking vacuum, it is cooled to 100 DEG C, adds
Enter the carbamide of 10 mass parts, then be warming up to 130 DEG C of reaction 1.5h.After being again cooled to 100 DEG C, add the water of 100 mass parts,
To polyamide reducing urination aqueous solution.At 35 DEG C, add the chloropropylene oxide of 25 mass parts, and be to slowly warm up to 60 DEG C, react 3h, to obtain final product
To the polyamide contracting urea epoxy adduct aqueous solution that active constituent content is 50%, it is labeled as N-2.
Synthesis example 3 (polyamide contracting urea epoxy adduct)
Only replaced by spermidine spermidine mixture, chloropropylene oxide spent glycol diglycidyl ether replaces, and remaining is with closing
Becoming example 2, the active constituent content obtained is the polyamide contracting urea epoxy adduct aqueous solution of 50%, is labeled as N-3.
Commercially available effective ingredient is the KR-005 zirconium carbonate ammonium (Lishui City Kai Run Chemical Co., Ltd.) of 30%, is labeled as N-4.
Embodiment 1
The water of 300 mass parts is added in reactor, is warming up to 45 DEG C；It is sequentially added into the acidic protein of 2.5 mass parts parts
The bean cake of the protein content more than 20% of enzyme and 100 mass parts, regulate after stirring to pH value be 5, enzymolysis 45 minutes；Regulation
PH value is 8.5, then is separately added into part potassium sorbate of 2 mass parts and the water resistant reinforcing modifying agent 1 of 16 mass parts, and stirs all
Even.
Embodiment 2～10
Technical process is same as in Example 1, and concrete formula refers to table 1；Concrete technology condition refers to table 2.
Table 1 formula table (being mass fraction in table)
Table 2 process conditions table
| Embodiment | Temperature (DEG C) | Enzymolysis pH value | Enzymolysis time (min) | Whole pH value |
| 1 | 45 | 5 | 45 | 8.5 |
| 2 | 30 | 5.3 | 60 | 7.9 |
| 3 | 35 | 4.3 | 20 | 8.4 |
| 4 | 50 | 4 | 33 | 8.7 |
| 5 | 55 | 5.7 | 55 | 9.5 |
| 6 | 40 | 5.5 | 50 | 7.5 |
| 7 | 40 | 6.5 | 45 | 8.5 |
| 8 | 45 | 4.5 | 70 | 9.0 |
| 9 | 45 | 6.0 | 50 | 10 |
| 10 | 45 | 4.5 | 45 | 8.0 |
Comparative example 1
Except the water resistant reinforcing modifying agent 1 of 16 mass parts replaces with the PAE that 100 mass parts effective mass content are 12.5%
Outward, remaining is with embodiment 1.
Comparative example 2
In addition to the water resistant reinforcing modifying agent 2 of 10 mass parts replaces with the PAE that 80 mass parts effective mass content are 12.5%,
Remaining is with embodiment 4.
Comparative example 3
In addition to the water resistant reinforcing modifying agent 3 of 15 mass parts replaces with the PAE that 60 mass parts effective mass content are 12.5%,
Remaining is with embodiment 8.
The preparation of test sample:
The Performance Properties Evaluation of based Wood Adhesives uses seven layers of composite plate sample and medium density fibre board (MDF) sample.
Sample through gluing, cold pressing and prepared by the process such as hot pressing.Coating weight is 350g/m2(two-sided), pressure of colding pressing is
1.2MPa, time are 50min, and hot pressing temperature is 135 DEG C, pressure is 1.4MPa, the time is 75s/mm, and after hot pressing, room temperature is displayed
24h。
Performance evaluation:
1) bin stability of based Wood Adhesives
The test of based Wood Adhesives bin stability is with reference to GB/T 14074-2006 " wood adhesive and resin inspection thereof
Method " in 3.9 regulation methods, treatment temperature is 60 ± 2 DEG C, but counts the most accordingly for protein gluing developing agent storage natural law
Calculate formula, only with record time t as reference, t the biggest explanation bin stability is the best, and unit is h.
2) dry strength of composite plate sample and wet strength
According to the regulation of 4.15.3 in GB/T17657-1999 " test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels "
Composite plate sample is tailored into A type sample, then according to regulation test sample moisture content, the sample ability that moisture content is qualified
Using the omnipotent mechanics machine of timber to measure bonding strength, unit is MPa.Dry strength is directly surveyed by the sample that moisture content is qualified
, wet strength by the qualified sample of moisture content through 4.15.4.2b) in the condition of regulation process after record.Test result is equal
Value, the bonding strength of test result numerical value the biggest explanation adhesive is the best.
3) the dipping and stripping performance of composite plate sample
According to the regulation of 4.17.3 in GB/T17657-1999 " test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels "
Style is tailored into given size, sample is through 4.17.4.1b) in after the condition of regulation processes, test is peeled off or layered portion
Length, unit is mm.Test result is average, and test result more novel bright adhesive water resistance is the best.
4) internal bond strength of medium-density plate sample
Will examination according to the regulation of 4.8 in GB/T17657-1999 " test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels "
Sample is tailored into given size, tests according to the method in 4.8.4.Test result is average, the biggest theory of test result numerical value
The internal bond strength of bright adhesive is the best.
5) free formaldehyde content
According to 4.12 Form aldehyde release in GB/T17657-1999 " test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels "
The regulation that amount condensed steam water measures is tested.
Test result
Table 3 performance test table
These are only the specific embodiment of the present invention, but the technical characteristic of the present invention is not limited thereto.Any with this
Based on bright, for realizing essentially identical technique effect, done ground simple change, equivalent or modification etc., all contain
Among protection scope of the present invention.
Claims (6)
1. a timber by water-fast bio-based without aldehyde adhesive, it is characterised in that include according to mass fraction:
Described water resistant reinforcing modifying agent is selected from polyhydric alcohol and in the condensation polymer of dialdehyde, polyamide contracting urea epoxy adduct
Plant or its mixture；
Described polyhydric alcohol is sorbitol；Described dialdehyde is glutaraldehyde；
Described polyamide contracting urea epoxy adduct obtains through procedure below: 1) polyamine is condensed with binary acid, and 2) condensation product
With urea-based compound deamination, 3) deamination products and epoxy polyfunctionality compound open loop addition；
Described polyamine is spermidine or it is with diethylenetriamine, triethylene tetramine, TEPA, spermine, ethylenediamine, corruption
The mixture of one or more in amine, cadaverine；Described binary acid is adipic acid；Described urea-based compound is carbamide；Described
Epoxy polyfunctionality compound is the one in chloropropylene oxide and Ethylene glycol diglycidyl ether.
Timber the most according to claim 1 by water-fast bio-based without aldehyde adhesive, it is characterised in that: described containing protein
Material is preferably the bean cake of protein content more than 20%.
Timber the most according to claim 1 by water-fast bio-based without aldehyde adhesive, it is characterised in that: described enzyme is
The mixture of one or more in acid protease, cellulase and amylase.
Timber the most according to claim 1 by water-fast bio-based without aldehyde adhesive, it is characterised in that: described preservative is
One in potassium sorbate, dodecyl dimethyl benzyl ammonium chloride or its mixture.
Timber the most according to claim 1 by water-fast bio-based without aldehyde adhesive, it is characterised in that: described fill material
For the one in chitosan, modified starch and kieselguhr or its mixture.
Timber the most according to claim 1 is by water-fast bio-based without aldehyde adhesive, and its preparation method is as follows: add water to anti-
Answer in still, be warming up to 30～55 DEG C；It is sequentially added into enzyme, soybean protein and fill material, regulates to pH value after stirring
It is 4～6.5, enzymolysis 20～70 minutes；Regulation pH value is 7.5～10, then is separately added into preservative and water resistant reinforcing modifying agent also
Stir.
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| CN112920771B (en) * | 2021-01-28 | 2022-03-25 | 山东农业大学 | Self-crosslinking cottonseed protein adhesive and preparation method thereof |
| CN117402571B (en) * | 2023-11-28 | 2024-03-08 | 西南林业大学 | Biomass starch adhesive and preparation method and application thereof |
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| CN101448910A (en) * | 2006-04-14 | 2009-06-03 | 国家淀粉及化学投资控股公司 | Aqueous biopolymer-containing labeling adhesive |
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| US20130156884A1 (en) * | 2011-12-19 | 2013-06-20 | Triarco Industries | Protease enzymes for increased protein digestion rate and absorption and methods of using the same |
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|---|---|---|---|---|
| CN101448910A (en) * | 2006-04-14 | 2009-06-03 | 国家淀粉及化学投资控股公司 | Aqueous biopolymer-containing labeling adhesive |
Non-Patent Citations (1)
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| 不同防腐剂对大豆胶粘剂防腐性能的影响;陈奶荣等;《福建林学院学报》;20090115(第01期);第53-56页 * |
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