CN100509904C - Brassiere pad - Google Patents
Brassiere pad Download PDFInfo
- Publication number
- CN100509904C CN100509904C CNB200480033331XA CN200480033331A CN100509904C CN 100509904 C CN100509904 C CN 100509904C CN B200480033331X A CNB200480033331X A CN B200480033331XA CN 200480033331 A CN200480033331 A CN 200480033331A CN 100509904 C CN100509904 C CN 100509904C
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- polyols
- weight polyols
- difference
- brassiere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn - After Issue
Links
Abstract
A flexible polyurethane foam inhibited from discoloring which is obtained by foaming materials for a polyurethane which comprise a polyol ingredient and an isocyanate. The polyol ingredient comprises two or more polyols differing in molecular weight, and the difference in molecular weight between the polyol having the highest molecular weight and the polyol having the lowest molecular weight is 500 or larger. Due to the use of a high-molecular polyol/low-molecular polyol mixture having a molecular-weight difference of 500 or larger as the polyol ingredient, a flexible polyurethane foam which is inhibited from discoloring, i.e., which has excellent unsusceptibility to discoloration, can be obtained without the need of using an expensive antioxidant and an expensive ultraviolet absorber or without the need of using an expensive aliphatic isocyanate or alicyclic isocyanate inferior in detergent resistance and long-lasting heat resistance. By using an antioxidant and an ultraviolet absorber, a further improvement in unsusceptibility to discoloration can be attained to thereby provide a flexible polyurethane foam which is more inhibited from discoloring.
Description
Technical field
The present invention relates to not allochroic flexible urethane foam, particularly as the not allochroic flexible urethane foam of dress materials such as brassiere gasket, shoulder pad, clothes hanger liner with health subsidiary material, bedding, medical treatment product, other various groceries raw materials etc. such as liner, paper nappy, sanitary towels.
Background technology
Flexible urethane foam has good resiliency, subside after using for a long time or repeatedly unlike cotton, and it is soft, has good sense of touch, so be widely used as health subsidiary material, bedding, medical treatment product, other various groceries raw materials etc. such as dress materials such as brassiere gasket, shoulder pad, clothes hanger liner cushioning material, paper nappy, sanitary towel.
Flexible urethane foam in the past is because the polyvalent alcohol raw material that is used for making contains the BHT (butylated hydroxytoluene) as antioxidant, so there is the problem of the porous plastics variable color (flavescence) that this BHT causes.When making the urethane raw foaming that contains BHT, residual BHT in the porous plastics after the foaming, the oxynitride (NO that contains in this BHT and the atmosphere
X) reaction, make the flavescence of urethane foam own.Flexible urethane foam itself also might be because of NO
XAnd variable color.
Flexible urethane foam is also because of ultraviolet influence flavescence.The variable color of UV-induced flexible urethane foam is that the phenyl ring in the compound that contains owing to urethane raw quinoneization takes place under action of ultraviolet ray causes.
The flavescence of flexible urethane foam and the migration variable color that causes thus are (near the cloth of porous plastics etc. owing to the porous plastics flavescence is colored, cause variable color), as the flexible urethane foam of daily necessities purposes such as dress material or bedding, medical treatment, other groceries the time, become serious defective.
Because NO
XBe present in the atmosphere, can not it is isolated fully, so prevent NO
XThe porous plastics flavescence that causes and be important by the migration variable color that it causes.
In the past, in order to prevent the variable color of aforesaid porous plastics, the specific antioxidant or the scheme (spy opens flat 11-323126 communique) of UV light absorber had been proposed in urethane raw, to cooperate.
Also proposed to use aliphatic isocyanates or alicyclic isocyanate to replace becoming the scheme (spy opens flat 10-36543 communique) of the aromatic isocyanate that contains phenyl ring that ultraviolet ray causes the reason of variable color.
But it is very high that the spy opens the specific antioxidant or the UV light absorber price that cooperate in the flat 11-323126 communique, cooperates above-mentioned substance to cause the raw materials cost costliness.And, if cooperate above-mentioned antioxidant or UV light absorber in a large number, then be difficult to the control reaction.
Though use the replacement of aliphatic isocyanates or alicyclic isocyanate to contain the flexible urethane foam discoloration-resistant excellence of the aromatic isocyanate of phenyl ring, but cost an arm and a leg, and heat-resisting weather resistance reduces, the deterioration that sanitising agent causes is serious, is not suitable for purposes such as dress material or bedding.
Summary of the invention
The not allochroic flexible urethane foam that the purpose of this invention is to provide sanitising agent weather resistance or heat-resisting excellent in te pins of durability.
Not allochroic flexible urethane foam of the present invention is the urethane foam that the urethane raw foaming that contains polyhydroxy reactant and isocyanic ester is formed, it is characterized in that, this polyhydroxy reactant contains the different polyvalent alcohol more than 2 kinds or 2 kinds of molecular weight, and the difference of the molecular weight of the low molecular weight polyols of the high molecular weight polyols of molecular weight maximum and molecular weight minimum is more than or equal to 500.
Embodiment
Describe the preferred version of not allochroic flexible urethane foam of the present invention below in detail.
In not allochroic flexible urethane foam of the present invention, use the polyhydroxy reactant of the different polyvalent alcohol of molecular weight more than 2 kinds or 2 kinds as urethane raw.The difference of the molecular weight of the low molecular weight polyols of the high molecular weight polyols of molecular weight maximum and molecular weight minimum is more than or equal to 500 in the polyhydroxy reactant.If the molecular weight differences less than 500 of the molecular weight of high molecular weight polyols and low molecular weight polyols, then can not obtain using the different polyvalent alcohol of molecular weight and the discoloration-resistant that produces improve effect.The difference of this molecular weight is more than or equal to 500, is preferably greater than or equals 2000, more preferably more than or equal to 3000.It is excessive that the difference of this molecular weight is crossed the molecular weight of ambassador's high molecular weight polyols, or the molecular weight of low molecular weight polyols is too small, and causing does not have versatility, so, the difference of molecular weight is less than or equal to 9600, more preferably is less than or equal to 7500, further preferably is less than or equal to 7000.
Difference by mix using molecular weight more than or equal to 500 high molecular weight polyols and low molecular weight polyols as polyhydroxy reactant, needn't use expensive antioxidant or UV light absorber, in addition, also needn't use high price and cause anti-sanitising agent or the aliphatic isocyanates or the alicyclic isocyanate of the reduction of heat-resisting weather resistance, just can obtain the not allochroic flexible urethane foam of discoloration-resistant excellence.
As mentioned above, also indeterminate by using the different polyvalent alcohol of molecular weight more than 2 kinds or 2 kinds can obtain the detailed reason of discoloration-resistant, but infer and be the molecular structure by changing urethane or arrange and improve discoloration-resistant.
As polyvalent alcohol, can use 2 kinds of polyvalent alcohols that molecular weight is different, also can use the different polyvalent alcohol of molecular weight more than 3 kinds or 3 kinds.When using the polyvalent alcohol more than 3 kinds or 3 kinds, as long as the difference of the molecular weight of the polyvalent alcohol of the polyvalent alcohol of molecular weight maximum and molecular weight minimum is more than or equal to 500.
As long as the difference of the molecular weight of high molecular weight polyols and low molecular weight polyols is more than or equal to 500, molecular weight to each polyvalent alcohol is not particularly limited, generally, the molecular weight of high molecular weight polyols is 2000～10000, be preferably 3000～8000 especially, the molecular weight of low molecular weight polyols is 80～9500, is preferably 400～1000 scope especially.
For the proportioning of high molecular weight polyols in the polyvalent alcohol and low molecular weight polyols, because when the relative high molecular weight polyols of low molecular weight polyols is very few, can't fully obtain mixing the use effect of the present invention that above-mentioned substance obtained, so, the ratio of the high molecular weight polyols in the preferred polyol is 30 weight %～99.5 weight %, the ratio of the low molecular weight polyols in the polyvalent alcohol is 0.5 weight %～70 weight %, the ratio of the high molecular weight polyols in the special preferred polyol is 50 weight %～97 weight %, the ratio of the low molecular weight polyols in the polyvalent alcohol is 3 weight %～50 weight %, and the scope of high molecular weight polyols: low molecular weight polyols=1:0.03～1 (weight ratio).
Kind to polyvalent alcohol is not particularly limited, and can use the polyether polyol or the polyester polyol that are used as the flexible urethane foam raw material usually.The OH value of the polyvalent alcohol that uses is generally 20～1500, and the OH value of preferred especially high molecular weight polyols is generally 20～60, and the OH value of low molecular weight polyols is generally 100～1500.
Flexible urethane foam of the present invention can also be following common urethane raw proportioning except that using the different polyvalent alcohol of molecular weight more than 2 kinds or 2 kinds as the polyhydroxy reactant as mentioned above.In order to make flexible urethane foam of the present invention, can use above-mentioned raw materials, foam according to conventional methods.The nco index of urethane raw (index) preferred 90～120.＜urethane raw proportioning (weight part) 〉
Polyhydroxy reactant: 100
Isocyanate prepolymer composition: 90～120 (nco indexs)
Catalyzer: 0.01～2.0
Whipping agent: 1.0～25.0
Surfactant: 0.1～3.0
Isocyanate prepolymer composition is the organic polymeric polyisocyanate that has 2 or 2 above isocyanate group in a part, can use the modifier of aliphatic category and aromatic poly-isocyanate compound, above-claimed cpd, but be not limited thereto.As the aliphatic category polymeric polyisocyanate, can enumerate hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, methylcyclohexane diisocyanate etc.As aromatic poly-isocyanate, can enumerate tolylene diisocyanate, diphenylmethanediisocyanate, poly-diphenylmethanediisocyanate etc.As the modifier of above-claimed cpd, can enumerate carbodiimide modified thing, prepolymer modifier.Preferred polymeric polyisocyanate is the modifier of aromatic series class polymeric polyisocyanate or aromatic series class polymeric polyisocyanate among the present invention, preferred especially tolylene diisocyanate, diphenylmethanediisocyanate.
As whipping agent, can use all whipping agents that are used to make urethane foam.For example, as inert, comprise fluoride compounds such as trichlorofluoromethane, Refrigerant 12 etc.; Material as utilizing methylene dichloride, liquefied carbon dioxide gas generated reactive gas comprises water, acid amides, nitro-paraffin etc.; Material as thermolysis generation gas comprises sodium bicarbonate, volatile salt etc.Wherein, as preferred blowing agent, can enumerate methylene dichloride, water etc.
As surfactant, can use silicone oil.
As catalyzer, can use all catalyzer that are generally used for making urethane foam.For example, can enumerate tin class catalyzer such as dibutyl tin dilaurate, stannous octoate; Tertiary amines such as triethylamine, 4-methyl hexamethylene diamine etc.
As required, the present invention can also be in urethane raw matching surface promoting agent or fire retardant, other auxiliary agents.Can enumerate silicon class tensio-active agent as tensio-active agent.As fire retardant, can use three (2-chloroethyl) phosphoric acid ester, three (2, the 3-dibromopropyl) known in the past fire retardant such as phosphoric acid ester in addition, can also use the type organic powder or the inorganic material powders such as metal hydroxides, ANTIMONY TRIOXIDE SB 203 99.8 PCT of urea, thiocarbamide.
As other auxiliary agents, can enumerate powder such as pigment end, talcum, graphite such as pigment, dyestuff, staple glass fibre, other inorganic extenders or organic solvent etc.
Even not allochroic flexible urethane foam of the present invention is not using aliphatic isocyanates or alicyclic isocyanate as isocyanic ester, and be to use the aromatic series kind isocyanate as isocyanic ester, mismatch under the situation of antioxidant or UV light absorber, still can obtain the discoloration-resistant excellence and based on the NO of JIS L 0855:1998
XThe difference of the YI value before and after the discoloration test is less than or equal to 70 flexible urethane foam.
But not allochroic flexible urethane foam of the present invention is not got rid of use antioxidant or UV light absorber, among the present invention, makes at least one side of containing antioxidant or UV light absorber in the urethane raw, can further improve discoloration-resistant.As mentioned above, this medicament costliness.In the present invention, by using the different polyvalent alcohol of molecular weight more than 2 kinds or 2 kinds, can obtain sufficient discoloration-resistant, therefore, can not contain in antioxidant or UV light absorber, particularly phenol antioxidant, benzotriazole category UV light absorber and the phosphoric acid class antioxidant any in fact.
In the present invention, though need not to cooperate antioxidant or UV light absorber just can obtain excellent discoloration-resistant, also can cooperate above-mentioned substance.By cooperating antioxidant or UV light absorber, the discoloration-resistant performance of urethane foam is further improved.So, can cooperate phenol antioxidant, benzotriazole category UV light absorber and phosphoric acid class antioxidant etc. according to the rank of desired discoloration-resistant.
The preferred foaming and molding of not allochroic flexible urethane foam of the present invention to density is 12～80kg/m
3
Utilize the present invention, can the cheap and reactive not allochroic flexible urethane foam that obtains not flavescence of porous plastics, anti-sanitising agent weather resistance, heat-resisting excellent in te pins of durability well.
Not allochroic flexible urethane foam of the present invention is useful as various dress materials such as brassiere gaskets with health subsidiary material such as liner, paper nappy, sanitary towel, bedding, medical treatment product, other various groceries raw materials etc., can provide at an easy rate not exist because the deterioration that causes of flavescence or outward appearance deterioration problem high-quality and product that commodity value is high.
Embodiment
Enumerate embodiment below and comparative example illustrates in greater detail the present invention.
Embodiment 1～4, comparative example 1～3
At 25 ℃ the urethane raw of proportioning shown in the table 1 is foamed according to ordinary method, make density and be about 25kg/m
3Flexible urethane foam.
This flexible urethane foam is carried out NO based on JIS L 0855:1998
XDiscoloration test before and after this test, is utilized Japan's electricity decorations society's system " ZE2000 ", measures the YI value of flexible urethane foam according to white plate benchmark based on JIS L 0855, and the result is as shown in table 1.At NO
XIn the discoloration test, the difference Δ YI of the YI value of the YI value of porous plastics and test back porous plastics is big more before the test, represents that variable color is big more, and Δ YI preferably is less than or equal to 40, especially preferably is less than or equal to 30, is more preferably less than or equals 25.
[table 1]
Notes 1～9 in the table 1 are as described below.
Annotate 1: Asahi Glass urethane (strain) system " EXCENOL4030 "
Polyether polyol
OH value=42
Molecular weight=4000
Annotate 2: the military field chemistry of Mitsui (strain) system " Actcall 32-160 "
Polyether polyol
OH value=160
Molecular weight=1000
Annotate 3: Sanyo changes into industry (strain) system " SANNIX GS-3000 "
Polyether polyol
OH value=56
Molecular weight=3000
Annotate 4: the military field chemistry of Mitsui (strain) system " Actcall FC-24 "
Polyether polyol
OH value=25
Molecular weight=7000
Annotate 5: the military field chemistry of Mitsui (strain) system " Actcall G-250 "
Polyether polyol
OH value=243
Molecular weight=700
Annotate 6: military field pharmaceutical industries (strain) system " TDI80 "
Tolylene diisocyanate
Annotate 7: flower king (strain) system " Kaolizer No.25 "
6-dimethylamino-1-hexanol
Annotate 8: SHIN-ETSU HANTOTAI's chemical industry (strain) system " F-242TB "
Silicon surfactant
Annotate 9: SHIN-ETSU HANTOTAI's chemical industry (strain) system " methylene dichloride "
Methylene dichloride
As shown in Table 1, the present invention is by using 2 kinds of polyvalent alcohols that molecular weight is different, can make Δ YI value and only use a kind of polyvalent alcohol relatively to reduce to below 1/3 or 1/3, even do not use antioxidant or UV light absorber, or aliphatic isocyanates or alicyclic isocyanate also can increase substantially discoloration-resistant.
Claims (12)
1, a kind of brassiere gasket, this brassiere gasket is made of urethane foam, this urethane foam is that the urethane raw foaming that contains polyhydroxy reactant and isocyanic ester is formed, it is characterized in that, this polyhydroxy reactant contains the different polyvalent alcohol of molecular weight more than 2 kinds or 2 kinds, the difference of the molecular weight of the low molecular weight polyols of the high molecular weight polyols of molecular weight maximum and molecular weight minimum is more than or equal to 500, and it is 12-80kg/m that this urethane foam plastic foaming is shaped to density
3, the isocyanate index of this urethane raw is 105-120.
2, brassiere gasket as claimed in claim 1 is characterized in that, the difference of described molecular weight is 500～9600.
3, brassiere gasket as claimed in claim 2 is characterized in that, the difference of described molecular weight is 2000-7500.
4, brassiere gasket as claimed in claim 3 is characterized in that, the difference of described molecular weight is 3000～7000.
5, brassiere gasket as claimed in claim 1 is characterized in that, the molecular weight of described high molecular weight polyols is 2000～10000, and the molecular weight of described low molecular weight polyols is 80-9500.
6, brassiere gasket as claimed in claim 5 is characterized in that, the molecular weight of described high molecular weight polyols is 3000～8000, and the molecular weight of described low molecular weight polyols is 400-1000.
7, brassiere gasket as claimed in claim 1 is characterized in that, the content of the described high molecular weight polyols in the polyhydroxy reactant is 30 weight %～99.5 weight %, and the content of described low molecular weight polyols is 0.5 weight %～70 weight %.
8, brassiere gasket as claimed in claim 7 is characterized in that, the content of the described high molecular weight polyols in the polyhydroxy reactant is 50 weight %～97 weight %, and the content of described low molecular weight polyols is 3 weight %～50 weight %.
9, brassiere gasket as claimed in claim 1 is characterized in that, the described high molecular weight polyols in the polyhydroxy reactant and the ratio of described low molecular weight polyols are in the scope of high molecular weight polyols: low molecular weight polyols=1:0.03～1 (weight ratio).
10, brassiere gasket as claimed in claim 1 is characterized in that, the OH value of high molecular weight polyols is 20～60, and the OH value of low molecular weight polyols is 100～1500.
11, brassiere gasket as claimed in claim 1 is characterized in that, described isocyanic ester is the aromatic series kind isocyanate.
12, brassiere gasket as claimed in claim 1 is characterized in that, is less than or equal to 70 based on the difference of the YI value before and after the NOx discoloration test of JIS L 0855:1998.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003382727 | 2003-11-12 | ||
| JP382727/2003 | 2003-11-12 | ||
| JP036497/2004 | 2004-02-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1878813A CN1878813A (en) | 2006-12-13 |
| CN100509904C true CN100509904C (en) | 2009-07-08 |
Family
ID=37510735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200480033331XA Withdrawn - After Issue CN100509904C (en) | 2003-11-12 | 2004-11-01 | Brassiere pad |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100509904C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125173A1 (en) * | 2010-04-06 | 2011-10-13 | 黒田 暢夫 | Migration-proof decorative piece constituted of thermoplastic synthetic resin |
| CN104974326B (en) * | 2014-04-03 | 2017-12-26 | 万华化学集团股份有限公司 | A kind of composition for preparing non yellowing flexible polyurethane foams, non yellowing flexible polyurethane foams and preparation method thereof |
| JP6762016B2 (en) * | 2016-01-26 | 2020-09-30 | 株式会社Ａｓｍ | A composition for polyurethane foam containing polyrotaxane, a polyurethane foam derived from the composition, and a method for producing a polyurethane foam. |
| JP6793249B2 (en) * | 2017-03-31 | 2020-12-02 | 三井化学株式会社 | How to make flexible polyurethane foam, clothing materials, brassiere pads, brassiere cups, and flexible polyurethane foam |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4525491A (en) * | 1982-12-24 | 1985-06-25 | Asahi Glass Company, Ltd. | Process for producing a polyurethane elastomer by reaction injection molding |
-
2004
- 2004-11-01 CN CNB200480033331XA patent/CN100509904C/en not_active Withdrawn - After Issue
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4525491A (en) * | 1982-12-24 | 1985-06-25 | Asahi Glass Company, Ltd. | Process for producing a polyurethane elastomer by reaction injection molding |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1878813A (en) | 2006-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1328298C (en) | Polyurethane compounds and articles prepared therefrom | |
| KR20070115509A (en) | Manufacturing method of non-yellowing flexible polyurethane foam with high resilience and durability | |
| CN101580575A (en) | Soft urethane foam and preparation method thereof | |
| US20060142529A1 (en) | Hydrophilic polyurethane polymers derived from a mdi-based isocyanate-terminated prepolymer | |
| KR20060099432A (en) | Process for preparing a visco-elastic polyurethane foam | |
| US4786704A (en) | Polyurea dispersions in organic isocyanates | |
| AU679730B2 (en) | Polymer polyols | |
| EP0679671B1 (en) | Flexible polyurethane foam and process for preparing same | |
| JP4977941B2 (en) | Pad made of hard yellowing soft polyurethane foam | |
| CN100509904C (en) | Brassiere pad | |
| KR19990071778A (en) | Process for producing flexible polyurethane foam | |
| JP5186735B2 (en) | Hard yellowing soft polyurethane foam and pad | |
| US20060247325A1 (en) | Flexible polyurethane foam inhibited from discoloring | |
| EP0358328A1 (en) | Novel isocyanate-prepolymer compositions | |
| JP5211809B2 (en) | Hard yellowing soft polyurethane foam and pad for clothing | |
| KR101225580B1 (en) | Aqueous polyurethane dispersed solution for sizing agent and method for processing thereof, and the sizing agent for glass fiber containing the same | |
| JP2002322236A (en) | Method for producing soft polyurethane slab foam | |
| JP2009242996A (en) | Hardly yellowing garment pad | |
| JP4597773B2 (en) | Method for producing flexible polyurethane foam | |
| JP3937811B2 (en) | Method for producing flexible polyurethane foam | |
| JPS5840316A (en) | High molecular modified polyol, production and manufacture of polyurethane product | |
| JP4495296B2 (en) | Polyurethane foam | |
| JP5501163B2 (en) | Method for producing flexible polyurethane foam | |
| JP3504770B2 (en) | Flexible polyurethane foam and method for producing the same | |
| JP3312476B2 (en) | Method for producing flexible urethane foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| AV01 | Patent right actively abandoned | ||
| AV01 | Patent right actively abandoned | ||
| AV01 | Patent right actively abandoned |
Granted publication date: 20090708 Effective date of abandoning: 20210707 |
|
| AV01 | Patent right actively abandoned |
Granted publication date: 20090708 Effective date of abandoning: 20210707 |