CN105142609B - Shower cosmetic agent and cosmetic agent box - Google Patents
Shower cosmetic agent and cosmetic agent box Download PDFInfo
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- CN105142609B CN105142609B CN201380074447.7A CN201380074447A CN105142609B CN 105142609 B CN105142609 B CN 105142609B CN 201380074447 A CN201380074447 A CN 201380074447A CN 105142609 B CN105142609 B CN 105142609B
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- cosmetic agent
- shower
- peg
- ppg
- box
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0216—Solid or semisolid forms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8129—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
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- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03C—DOMESTIC PLUMBING INSTALLATIONS FOR FRESH WATER OR WASTE WATER; SINKS
- E03C1/00—Domestic plumbing installations for fresh water or waste water; Sinks
- E03C1/02—Plumbing installations for fresh water
- E03C1/04—Water-basin installations specially adapted to wash-basins or baths
- E03C1/046—Adding soap, disinfectant, or the like in the supply line or at the water outlet
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D40/00—Casings or accessories specially adapted for storing or handling solid or pasty toiletry or cosmetic substances, e.g. shaving soaps or lipsticks
- A45D2040/0093—Casings or accessories specially adapted for storing or handling solid or pasty toiletry or cosmetic substances, e.g. shaving soaps or lipsticks storing soluble solid substances and suitable for application after adding a liquid solvent, e.g. water
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Dermatology (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Cosmetics (AREA)
Abstract
A kind of shower cosmetic agent contains polyethylene glycol (PEG)/polypropylene glycol (PPG) copolymer as neccessary composition.The shower preferably comprises polyvinyl alcohol (PVA), further preferably enamel with cosmetic agent.According to this constitution, in addition to may insure that there is certain stripping quantity to cold water or warm water, and excessive dissolubility can be inhibited and obtain the sufficient duration of solid shape.
Description
Technical field
The present invention relates to a kind of releasably interior cosmetic agent box for being set to shower head and it is incorporated in the cosmetic agent box
Shower cosmetic agent.
Background technology
In general, be filled in the cosmetic agent box of the shower set by bathroom or face washing cabinet finish, moisturizer,
The cosmetic agents ingredients such as fragrance, balneation agent.Then, these cosmetic agent ingredients are from dissolution in cosmetic agent box in cold water or in warm water,
And it spreads out from shower head.Cosmetic agent ingredient usually with solid or it is powdered be filled in cosmetic agent box, but due to be easy
It is dissolved in cold water or warm water, so can in a relatively short period of time be dissolved in cold water or warm water, solid shape, which does not have, to be continued
Property, and then its effect does not have duration.Therefore, it has to cosmetic agent ingredient is continually supplemented into cosmetic agent box, it is quite numb
It is tired.The cosmetic agent of the duration of solid shape is inhibited and had therefore, it is necessary to a kind of dissolubility in cold water or warm water
Ingredient.
Patent Document 1 discloses this solid-states to wash one's hair bathpreparation.The solid-state is washed one's hair bathpreparation and is contained selected from pigment, perfume (or spice)
Material, balneation agent, remover and change a kind of make-up product or the polyethylene glycol of more than one ingredient and 30-95 mass %.As
Polyethylene glycol is, it is preferable to use average molecular weight is the polyethylene glycol of 1000-6000.Also, by using the solid-state shower system
Product, it is elongated to the dissolution time of cold water or warm water that solid-state washes one's hair bathpreparation, can make pigment, fragrance, balneation agent, remover and
Change make-up product equably to dissolve out.
Existing technical literature
Patent document
Patent document 1:Japanese Patent Publication 2-7571 bulletins
Invention content
Problems to be solved by the invention
In the solid-state of the existing composition described in above-mentioned patent document 1 washes one's hair bathpreparation, using polyethylene glycol, as
Inhibit the deliquescent ingredient for water.But dissolubility of the polyethylene glycol for water compared with polypropylene glycol etc. is higher.Cause
This, is filled in cosmetic agent box in cosmetic agent ingredient in use, the dissolubility to water is relatively high, especially to 35 DEG C or more
Warm water dissolubility higher.Therefore, bathpreparation is washed one's hair as the solid-state for cosmetic agent box, the duration of solid shape is inadequate
Fully.
It is made currently invention addresses such problems of the prior art.Its purpose is to provide a kind of shower use
Cosmetic agent in addition to may insure there is certain stripping quantity to cold water or warm water, and can inhibit excessive dissolubility and obtain
The sufficient duration of solid shape.
Means for solving the problems
In order to achieve the above objectives, shower of the invention cosmetic agent includes polyethylene glycol (hereinafter referred to as PEG)/poly- third
The copolymer of glycol (hereinafter referred to as PPG) is as neccessary composition.
Preferably, shower cosmetic agent includes polyvinyl alcohol (hereinafter referred to as PVA).
It is further preferred that shower cosmetic agent includes enamel.
Preferably, the PEG/PPG copolymers, PVA or enamel are uniformly dispersed, and are solid-like in room temperature.
Preferably, the mass ratio (PEG/PPG) of the PEG in the PEG/PPG copolymers and PPG be (150-200)/
(35-70)。
Preferably, the PVA is the partly-hydrolysed PVA that saponification degree is 86-90 moles of %.
Preferably, the content of the PVA is 0.7-15 mass %.
Also, the cosmetic agent box of the present invention being accommodated in shower head has:Inflow entrance introduces cold water or warm water;Stream
Aquaporin, with the inflow entrance unicom;And cosmetic agent incorporating section, there is the receiving room of storage cosmetic agent, and with connection
Logical portion, for the portion of unicom by the receiving room and the pipelined channel unicom, making can by the cold water or warm water of the pipelined channel
Come in and go out the receiving room, and the shower cosmetic agent described in above-mentioned any one is accommodated in the cosmetic agent incorporating section.
Invention effect
According to the present invention, in addition to may insure that there is certain stripping quantity to cold water or warm water, and can inhibit excessive
Dissolubility can obtain sufficient duration.
Description of the drawings
Fig. 1 is the outside drawing of shower head, and Fig. 1 (a) is front view, and Fig. 1 (b) is right view.
Fig. 2 is the sectional view of shower head, and Fig. 2 (a) is the longitudinal sectional view of handle portion, and Fig. 2 (b) is different from Fig. 2 (a)
Partial cut handle portion longitudinal sectional view.
Fig. 3 is the figure of the internal structure for the handle portion for illustrating shower head, and Fig. 3 (a) is vertical view, and Fig. 3 (b) is stereogram.
Fig. 4 is the figure of the box set on shower head in explanation, and Fig. 4 (a) is the stereogram for the appearance for showing box, and Fig. 4 (b) is box
Sectional view.
Fig. 5 is the shower cosmetic agent for embodiment 1 and Comparative Examples 1 and 2, shows temperature and the shower of warm water
Figure of the adornment agent dissolution to the dissolution concentration relationship in warm water.
Reference sign
10 ... shower heads, 11 ... heads, 12 ... handle portions, 51 ... box shells, 51c ... openings (inflow entrance), 52 ... duckbilleds
Valve, 53 ... inner tubes (pipelined channel), 53c ... linked holes (portion of unicom), 54 ... medicine containing portions (cosmetic agent incorporating section), 100 ...
Shower cosmetic agent.
Specific implementation mode
Hereinafter, being described in detail to the embodiment for embodying the present invention.
It includes PEG/PPG copolymers as neccessary composition that cosmetic agent is used in shower.The shower is preferably included with cosmetic agent
PVA more preferably includes enamel.Also, shower cosmetic agent can also include other compositions.
Then, each ingredient of shower cosmetic agent is illustrated.
(PEG/PPG copolymers)
PEG/PPG copolymers have polyethylene glycol (Polyethylene glycol) unit and polypropylene glycol in the molecule
(Polypropylene glycol) unit, and be nonionic surfactant, there is moistening effect.It makes up as in shower
PEG/PPG copolymers used in agent are preferably the copolymer of solid at normal temperatures.
The PEG units for constituting the PEG/PPG copolymers have raising shower cosmetic agent in water (cold water or warm water)
Deliquescent function, PPG units, which have, inhibits deliquescent function of the shower cosmetic agent relative to water.Therefore, pass through tool
There are the both sides of these PEG units and PPG units, PEG units and PPG units to play synergistic effect, inhibit shower cosmetic agent
Dissolubility in cold water and warm water can realize the duration of dissolution.
The copolymerization ratio of PEG and PPG in PEG/PPG copolymers are not particularly limited.Therefore, as PEG/PPG copolymers,
The copolymer (digital representation mass ratio) that can be listed below.
PEG/PPG-3/17 copolymers, PEG/PPG-5/30 copolymers, PEG/PPG-5/35 copolymers, PEG/PPG-8/55
Copolymer, PEG/PPG-10/30 copolymers, PEG/PPG-10/65 copolymers, PEG/PPG-12/35 copolymers, PEG/PPG-
16/17 copolymer, PEG/PPG-20/9 copolymers, PEG/PPG-20/20 copolymers, PEG/PPG-20/60 copolymers, PEG/
PPG-22/25 copolymers, PEG/PPG-25/30 copolymers, PEG/PPG-30/35 copolymers, PEG/PPG-35/40 copolymers,
PEG/PPG-50/40 copolymers, PEG/PPG-150/35 copolymers, PEG/PPG-160/30 copolymers, PEG/PPG-190/60
Copolymer, PEG/PPG-200/40 copolymers, PEG/PPG-200/70 copolymers, PEG/PPG-240/60 copolymers, PEG/
PPG-300/55 copolymers.
In the example of above-mentioned copolymer, copolymerization ratio is preferably PEG/PPG (mass ratio)=(150-200)/(35-70's)
In range.If the copolymerization ratio be more than 150/35 so that PEG shared by percentage become larger, shower cosmetic agent can be shown in cold water
And the tendency that dissolubility in warm water is excessively high.On the other hand, if copolymerization ratio makes the percentage of PEG become smaller less than 200/70,
Dissolubility of the shower cosmetic agent in cold water and warm water can be then set to become to be not enough.
Incidentally, the solidification point for the copolymer that PEG/PPG mass ratioes are 150/35 is 52 DEG C, and PEG/PPG weight ratios are
The solidification point of 200/70 copolymer is 55 DEG C.
Also, if the molecular weight (degree of polymerization) of PEG/PPG copolymers is got higher, although shower cosmetic agent is in cold water or warm water
In dissolution rate be suppressed, swelling is also suppressed, but using shower cosmetic agent when sense of touch (slippery feeling) be deteriorated, institute
The molecular weight for suitably setting PEG/PPG copolymers to need to consider these factors.
(PVA)
PVA is due to multiple hydroxys, so having very strong hydrophily, especially having and dissolving in warm water in this way
Characteristic.Therefore, by shower with mixing PVA in cosmetic agent, to more particularly to improve shower cosmetic agent 35 DEG C with
On warm water in dissolubility.
The PVA can be obtained by the saponification of polyvinyl acetate, and can be shown with following chemical formula.
-〔CH2-CH(OH)〕m-〔CH2-CH(OCOCH3)〕n
Here, the degree of polymerization of PVA is m+n, saponification degree is m/ (m+n).
As the PVA used in shower cosmetic agent, from the dissolubility in warm water can be improved, and can inhibit
For bloating tendency viewpoint, preferably partly-hydrolysed PVA, saponification degree is preferably 86-90 moles of %, and the degree of polymerization is preferably 1800-
2000.In the case where saponification degree is less than 86 moles of % or the degree of polymerization is less than 1800, shower cosmetic agent is for cold water or warm water
The tendency of swelling becomes strong, so undesirable.On the other hand, the case where saponification degree is more than 90 moles of % or the degree of polymerization is more than 2000
Under, shower cosmetic agent reduces the dissolubility of cold water or warm water, so undesirable.
(enamel)
As enamel, collagen, ceramide, placental hormone, various vitamins (Vitamin C, vitamin can be enumerated
E etc.), natural perfume material, synthetic perfume, compound perfume (perfume etc.), finish, moisturizer, fragrance, deodorant, antiperspirant, pigment,
Preservative, emulsifier, amino acid, water etc..The type of enamel does not limit, and can also use other published enamels.
By comprising the PEG/PPG copolymers and PVA, to which enamel will not be lavishly molten from shower cosmetic agent
Go out, enamel can be made to dissolve out for a long time.
(other additive components)
As other additive components, viscosity modifier, excipient etc. can be suitably selected.
(component of shower cosmetic agent)
The PEG/PPG copolymers for constituting shower cosmetic agent are the main component of shower cosmetic agent, are made up in shower
Percentage included in agent is preferably 80-97 mass %.If the content of PEG/PPG copolymers is less than 80 mass %, it is difficult to
Appropriate dissolubility of the shower cosmetic agent in cold water or warm water is obtained, and is also difficult to obtain moisture retention.On the other hand, if
The content of PEG/PPG copolymers is higher than 97 mass %, then the content of PVA or enamel relatively reduces, and cannot obtain based on this
The effect of a little ingredients, so undesirable.
Also, it is preferred that the PVA containing 0.7-15 mass % in shower cosmetic agent, more preferably contains 3.5-15 matter
Measure the PVA of %.In the case where the content of PVA is less than 0.7 mass %, contact cold water or temperature when using shower cosmetic agent
When water, takes a shower and become strong with the tendency of cosmetic agent swelling, so undesirable.On the other hand, in the content of PVA more than 15 mass %'s
In the case of, the content of PEG/PPG copolymers and enamel relatively reduces, and plays the effect of these ingredients with being unable to fully,
So undesirable.
Also, in the shower enamel for preferably comprising 2-7 mass % in cosmetic agent.It is less than 2 matter in the content of enamel
In the case of measuring %, the moisture retention as enamel, armaticity and other effects cannot be fully played.On the other hand, in enamel
Content be more than 7 mass % in the case of, the content of PEG/PPG copolymers or PVA relatively reduce, the functions of these ingredients hair
Deficiency is waved, so unsatisfactory as shower cosmetic agent.
Further, in the case where mixing other additive components, other additive components in shower cosmetic agent
Content be preferably 5 mass % or less.If the content of other additive components is more than 5 mass %, above-mentioned each ingredient contains
Amount is reduced, and original function of shower cosmetic agent cannot be played, so undesirable.
Above-mentioned shower is incorporated in cosmetic agent in cosmetic agent box, and in order to be easy to be managed, at normal temperatures preferably
For solid-like.That is, in the case of the cleaning of body when shower is not used in shower with cosmetic agent, in order to maintain to wash one's hair
The shape of bath cosmetic agent, at normal temperatures preferably solid-like.And, it is preferable that by PEG/PPG copolymers, PVA and enamel
It is uniformly dispersed, in the case of capable of dissolving out when in use in this way, each ingredient is made equably to dissolve out.
(cosmetic agent box and shower head)
Then, based on Fig. 1-Fig. 4 to being mounted with the shower head of the cosmetic agent box (hreinafter referred to as box) 50 of embodiment
10 and the composition of box 50 illustrate.
As shown in Fig. 1 (a), (b), shower head 10 is made of head 11 and handle portion 12.Switching is provided on head 11
Portion 20, the switching part 20 is in order to make in runner 71,72 that water route 70 in handle portion 12 shows with Fig. 2 (a), (b), downstream side
Any one runner unicom and switched over operation.Runner 71,72 collaborates in the downstream side of switching part 20.The switching part 20
Have the 1st operating member 45 and the 2nd operating member 48.It is formed with multiple water sprayering holes 16 in the top end part on head 11.
As shown in Fig. 2 (a), (b), the box 50 is removably accommodated in the inside in the water route of the handle portion 12 70.
Water route 70 between the inner peripheral surface and the peripheral surface of box 50 of handle portion 12 is formed with water flowing gap 12c.Head 11 and handle portion
12, by screw part 12d connections, are screwed togather by releasing it, and the top in water route 70 is made to open, so as in handle portion 12
Load and unload box 50.
As shown in Fig. 3 (a), (b), multiple padded portion 12e are formed in the bottom in the downstream side in water route 70.As Fig. 2 (a),
(b) shown in, by the way that box 50 to be placed on the padded portion 12e, and cold water and warm water is made to be diffused into water route 70.In handle portion
12 inner peripheral surface is formed with multiple positioning floor 12f, and multiple positioning floor 12f engages with the peripheral surface of box 50, thus by box
50 are positioned at the center in water route 70.
As shown in Fig. 4 (a), (b), box 50 has cover 61.Box 50 has the box shell 51 of bottomed tube.In box shell
51 bottom wall is formed with multiple slit 51a.As shown in Fig. 4 (b), the valve of cylindrical shape is formed in the bottom wall central of box shell 51
Room 51b, valve chamber 51b and slit 51a unicom.Valve chamber 51b via the opening 51c being arranged on the top of valve chamber 51b and with
53 unicom of aftermentioned inner tube.Opening 51c is equivalent to inflow entrance, and inner tube 53 is equivalent to pipelined channel.
As shown in Fig. 2 (a), (b) and Fig. 4 (b), duckbill valve 52 is configured in valve chamber 51b, the duckbill valve 52 is as inverse
Only valve is played a role, is made of rubber elastomeric material.The top end part 52b of duckbill valve 52 is divided into two parts, the top
Portion's 52b Elastic Contacts.
As shown in Fig. 2 (a), (b) and Fig. 4 (b), it is configured with the inner tube 53 of cylindrical shape in the axle center part of box shell 51,
The lower part of the inner tube 53 is integrated with the valve chamber 51b.In inner tube 53, with predetermined in the overall length of circumferencial direction and length direction
Spacing is equipped with multiple linked hole 53c.Linked hole 53c is equivalent to portion of unicom.Between inner tube 53 and valve chamber 51b and box shell 51
Zoning has medicine containing portion 54.In the chimeric spout member 55 for having tubular of the end of downstream side of box shell 51, it is embedded in inside it
The end for having inner tube 53, to make 53 unicom of spout member 55 and inner tube.It is accommodated in the storage space in medicine containing portion 54
Water-soluble take a shower uses cosmetic agent 100, which is solid and is shaped generally as cylindrical shape.The medicament is received
The storage space in portion 54 received is equivalent to receiving room, and medicine containing portion 54 is equivalent to cosmetic agent incorporating section.Also, it makes up in shower
Under the original state that agent 100 is not dissolved, shower cosmetic agent 100 end of downstream side and spout member 55 lower end it
Between be formed with space 101.In the present embodiment, as shower cosmetic agent 100, the moisturizing for example containing moisturizing ingredient is used
Agent.Cold water or the warm water dissolving that the shower cosmetic agent 100 is introduced by the linked hole 53c via inner tube 53, are protected to generate
Wet liquid.Later, moisture retention liquid flows out to the outside of box 50 via spout member 55.
Netted strainer 57 is configured between the upper end and spout member 55 for the inner tube 53 that Fig. 4 (b) is shown.The strainer
57 are formed with multiple fine holes by formation such as metal meshes, in strainer 57.The strainer 57 is kept here to be divided by the medicament 100 of solid state
From and from linked hole 53c outflow particle, so as not to flowing out to 11 side of head.Strainer 57 as a whole be in fall cup-shaped, and
Downstream bulging to shower cosmetic agent 100.
Then, the cosmetic agent box of shower head and the effect of shower cosmetic agent that constitute in the above-described manner are said
It is bright.
Using the shower for not containing moisture retention liquid, as shown in Fig. 2 (a), user presses the 2nd operating member
48.If so, though omitting detailed description, the runner 71 of the water flowing gap sides 12c in water route 70 is opened, and
The runner 72 of 53 side of inner tube is closed, and so that cold water or warm water is managed via shower and flow to head 11 by water flowing gap 12c
Runner 71, and from water sprayering hole 16 spray.In this case, since the runner 72 in the downstream side of inner tube 53 occludes, so duck
Mouth valve 52 does not open, and water may not flow into the inside of the inner tube 53 of box 50.Therefore, in this state, duckbill valve 52 by itself
Elasticity and occlude, even if to valve closure if the hydraulic pressure in inner tube 53 is than the hydraulic pressure higher of upstream side of duckbill valve 52 pressure difference
Direction acts on duckbill valve 52.Therefore, it is possible to avoid the moisture retention liquid adverse current in inner tube 53 to the shower pipe of the outside of shower head 10
Side.
In the case where utilizing the shower containing moisture retention liquid, user presses the press section 45a of the 1st operating member 45.Cause
This, though not illustrating, runner 72 is opened.Therefore, cold water or warm water, which are more than from the water flowing gap 12c, flow to runner 71
Side so the duckbill valve 52 that Fig. 2 (a), (b) are shown is opened, and makes since the runner 72 of the upstream side of duckbill valve 52 is opened
Cold water or warm water flow into the inside of the inner tube 53 of box 50.Flow into inner tube 53 in cold water or warm water via inner tube 53 linked hole
53c flows into medicine containing portion 54.Flow to medicine containing portion 54 cold water or warm water by the medicament dissolution in medicine containing portion 54, and make
It becomes moisture retention liquid.Then, which flows out to from linked hole 53c in inner tube 53, via strainer 57 out of spout member 55
Flow into runner 72.
Moisture retention liquid in runner 72 in the downstream side of switching part 20 and the cold water being flow to from water flowing gap 12c in runner 71 or
Warm water mixes, and as the moisture retention liquid diluted.Then, the moisture retention liquid diluted is sprayed from water sprayering hole 16.In addition, valve chamber 51b
Though wall do not form hole, by shower cosmetic agent 100 dissolves make its volume reduce, to make to pass through linked hole
53c flows into the cold water or warm water in medicine containing portion 54 and forms turbulent flow around the shower cosmetic agent 100 after volume reduction, makes
Shower cosmetic agent 100 after volume is reduced floats.Therefore, even if the wall in valve chamber 51b does not form hole, shower makeup
Agent 100 also can suitably be dissolved and be flowed out from linked hole 53c.
In this way, operating the 1st operating member 45 and the 2nd operating member 48 by selectivity, can obtain without moisture retention liquid
Usually shower and the shower mode containing moisture retention liquid.In this case, it is set in a manner of it can obtain the moisture retention liquid of debita spissitudo
Determine the internal diameter of said inner tube 53, the size of the opening of linked hole 53c or quantity or allocation position etc..If so, it washes one's hair
Bath with cosmetic agent 100 by inflow medicine containing portion 54 cold water or warm water prune bit by bit, and moment be dissolved.
In addition, it is formed with space 101 with the downstream side of cosmetic agent 100 in shower, and in the upper of shower cosmetic agent 100
It is formed with interval between end and strainer 57, and strainer 57 is formed bulging shape in downstream side.Therefore, from shower cosmetic agent
The larger particle of 100 strippings can confusedly be moved in the upstream side of strainer 57 according to flow.It is such therefore, it is possible to prevent
Particle is attached to 57 inside of strainer and runner is made to be blocked.
Since shower uses cosmetic agent 100 to include PEG/PPG copolymers as neccessary composition, so can inhibit for cold water
Or the dissolubility of warm water, and realize certain dissolubility.Also, since shower includes PVA with cosmetic agent 100, so improving
Especially for the dissolubility of warm water.Moreover, the moisturizer by being used as enamel, can obtain good skin after shower
Moist feeling.
In this way, shower cosmetic agent 100 according to the present embodiment, can inhibit the excessive dissolution in cold water or warm water
Property while, can be dissolved out with stable state in long-time with certain stripping quantity.
(variation)
In the above-described embodiment, moisturizer is used as the medicament for being accommodated in box 50.It is accommodated in the medicament of box 50 not
Be only limitted to this, can also be perfume, weight reducing agent, the toner with whitening function, antiperspirant etc. other change make-up additives, use
In the medicament of whelk, atopic dermatitis, skin disease countermeasure.Also, solid and cylinder in the above-described embodiment, are used
The medicament of shape, but the shape of medicament or form are not limited to that.Such as gel or granular medicament can also be used
Deng.
In the above-described embodiment, in order to from 10 distribution water of shower head, water be made to may not flow into box 50,
It is provided with duckbill valve 52 in box 50.It can also be other than the duckbill valve 52 so that water is may not flow into the non-return valve of box when only spreading water
It constitutes.Also, in the case where only spreading water, as long as the composition that the solution for having dissolved medicament in box 50 does not flow out, so that it may with
The composition of box 50 is flowed into using water.
According to the embodiment, following effect can be obtained.
(1) shower of present embodiment use cosmetic agent using comprising PEG/PPG copolymers as being constituted in a manner of neccessary composition.
As a result, the synergistic effect of the PEG units and PPG units by PEG/PPG copolymers, it can be ensured that in cold water or warm water
While certain stripping quantity, excessive dissolubility can be inhibited and obtain the sufficient duration of solid shape.
(2) shower cosmetic agent is constituted in a manner of further including PVA.The solubility of PVA in water according to temperature and
Variation, the solubility in warm water are higher than cold water.Therefore, it by adjusting the additive amount of PVA, can adjust to cold water or warm water
The solubility of shower cosmetic agent entirety.Also, by adding PVA, the bloating tendency of shower cosmetic agent can be inhibited.
(3) shower cosmetic agent is constituted in a manner of further including enamel.Therefore, maintain shower cosmetic agent cold
Dissolubility appropriate in water or warm water, and moisture retention based on enamel, deodorization, hidroschesis, anti-corrosive properties can be played
And other effects.
(4) in the shower cosmetic agent of present embodiment, PEG/PPG copolymers, the PVA and the enamel are uniform
Ground disperses, and is at normal temperatures solid-like.As a result, these ingredient can be made equably to dissolve out when in use.
(5) mass ratio of the PEG in the PEG/PPG copolymers and PPG is (150-200)/(35-70).In this feelings
Under condition, dissolubility of the shower cosmetic agent to water and warm water can be inhibited, so as to improve duration.
(6) PVA is the partly-hydrolysed PVA that saponification degree is 86-90 moles of %.As a result, by adjusting partly-hydrolysed
The additive amount of PVA can further be easily adjusted shower cosmetic agent integrally to the solubility of cold water or warm water.Also, pass through
Partly-hydrolysed PVA is added, the bloating tendency of shower cosmetic agent can be inhibited.
(7) content of the PVA is 0.7-15 mass %.It is washed one's hair as a result, can be reduced when using shower cosmetic agent
Bath touches the possibility of cold water or warm water and swelling with cosmetic agent.It is more excellent according to embodiment 11 and embodiment 14,15, PVA
The content of choosing is 1-13 weight %.According to embodiment 2,9 and 10, the preferred contents of PVA are 3.5-7 mass %.
(8) the cosmetic agent box of present embodiment has:Be open 51c (inflow entrance), introduces cold water or warm water;Inner tube 53
(pipelined channel), with opening 51c unicom;And medicine containing portion 54 (medicine containing room), there are the receipts of storage cosmetic agent
It receives space (receiving room), and there is linked hole 53c (portion of unicom), linked hole 53c is by the storage space and the (stream of said inner tube 53
Aquaporin) unicom, and can make to come in and go out relative to the storage space by the cold water or warm water of inner tube 53 (pipelined channel), in medicine
Agent incorporating section 54 is accommodated with above-mentioned shower cosmetic agent 100.
As a result, according to the present embodiment, above-mentioned shower cosmetic agent can be suitably used, the shower cosmetic agent
It can ensure that there is certain stripping quantity to cold water or warm water, and inhibit excessive dissolubility and obtain the sufficient of solid shape
Duration.
Embodiment
Then, embodiment and comparative example are enumerated, the embodiment is further concretely demonstrated.
(embodiment 1 and Comparative Examples 1 and 2)
In embodiment 1, it will be mixed and be modulated by following manufacturing method with the ingredient of following a-d components and washed one's hair
Bath cosmetic agent.
(a)
92.15 mass % of PEG/PPG-150/35 copolymers
(b1) following 3 ingredients amount to 1.7 mass %
1,2- ethohexadiol (moisturizer), Sensiva SC50 (deodorant, antiperspirant), methyl p-hydroxybenzoate (preservative)
(b2) following 3 ingredients amount to 1.5 mass %
Amino acid, collagen, water
(c)
3.65 mass % of PVA
(d)
1.0 mass % of fragrance
(manufacturing method)
The manufacturing method of shower cosmetic agent is illustrated.
The material of said components a, b1, b2 are put into vacuum emulsification kettle, vacuum state of withing while with blade stirring adds
Heat makes it equably dissolve to 80 DEG C.In addition, heating temperature is 80 DEG C in the present embodiment, but as long as contributing to dissolve
Temperature appropriate.
Then, the material of component c being put into the kettle, vacuum state of withing while with blade stirring is heated to 80 DEG C,
It is stirred until homogeneous.The heating temperature is 80 DEG C in the present embodiment, but as long as contributing to the temperature appropriate being uniformly dispersed
.
Then, vacuum state of withing while with blade stirring is begun to cool, and predetermined temperature (such as 65 is reduced in temperature
DEG C or so) time point input component d material, continue to cool down while with blade stirring, become than the predetermined temperature
The time point of lower taking-out temperature takes out, and is configured to predetermined shape, to obtain shower cosmetic agent.The shower cosmetic agent
It is solid-like under room temperature (for example, 25 DEG C).In addition, as long as the temperature that the taking-out temperature is easy to take out from kettle is (in this reality
Apply in example is 65 DEG C), it is not particularly limited.
As long as the shape of shower cosmetic agent can be accommodated in the shape for the box for loading the shower cosmetic agent, not special
It does not limit.For example, the shape as the shower cosmetic agent that can be accommodated in the box, can select powder, granular, column, cylinder
The proper shapes such as shape.
On the other hand, in comparative example 1, the PEG/PPG-150/35 copolymers used in embodiment 1 are substituted, and are made
With the PEG homopolymers with the unit (block) roughly the same with the PEG units of PEG/PPG-150/35 copolymers.
Also, in comparative example 2, the PEG/PPG-150/35 copolymers used in embodiment 1 are substituted, and use has
The PPG homopolymers of the unit (block) roughly the same with the PPG units of PEG/PPG-150/35 copolymers.
In addition, in order to maintain identical condition, cosmetic agent in embodiment and comparative example is respectively shaped to cylinder
Shape.
(test method)
The shower of embodiment 1 and Comparative Examples 1 and 2 is filled to above-mentioned box 50 with cosmetic agent, by shower head with 9L/ points
The flow of clock sprinkles water 35 DEG C, 40 DEG C and 45 DEG C of warm water with following test cycle.That is, being tried at one
It tests in cycle, circulation warm water 1 minute places a hour at room temperature, then circulation warm water 15 minutes, 8 dry at 40 DEG C
After hour, the quality of measuring box 50, the decrement (g) of the cosmetic agent in measuring box 50, so as to find out dissolution concentration (ppm).And
And it the results are shown in table 1 and Fig. 5.
In Figure 5, ◇ indicates that embodiment 1, indicate that comparative example 1 and △ indicate comparative example 2.
(table 1)
It, in embodiment 1, independently with the temperature of warm water, can be by shower cosmetic agent as shown in table 1 and Fig. 5
It dissolves out concentration and inhibits the low concentration as 13.4-36.9ppm.On the other hand, in the case of the PEG of comparative example 1, warm water
Dissolution concentration indicates high dissolution concentration as 41.3ppm when temperature is 35 DEG C, and dissolving out concentration at 45 DEG C rises to
89.2ppm.Also, in the case of PPG in comparative example 2, when the temperature of warm water is 35 DEG C dissolution concentration indicate 22.9ppm this
The relatively low dissolution concentration of sample, but dissolve out concentration at 40 DEG C and steeply rise to 80.3ppm, concentration is dissolved out at 45 DEG C to be reached
Result as 112.3ppm.
Then, for the embodiment 1 and the shower cosmetic agent of Comparative Examples 1 and 2, the sense of touch measured in taking a shower is (lubricious
Sense), it is dry after moisturizing sense and solid shape duration, and these results are shown in table 2.
(table 2)
Sense of touch in shower use | Moisturizing sense after drying | Solid shape duration | |
Embodiment 1 | ○ | ○ | ○ |
Comparative example 1 | × | △ | ○ |
Comparative example 2 | ○ | × | × |
Zero ... is good, △ ... is substantially good, × ... it is unchanged or shape cannot be maintained
As shown in table 2, in embodiment 1, the sense of touch in shower use, it is dry after moisturizing sense and solid shape hold
Any one of continuous property, not swelling due to water has obtained good result.On the other hand, the PEG's of comparative example 1
In the case of, although solid shape can continue, the adjustment of the dissolution concentration to warm water cannot be carried out, cannot obtain taking a shower uses
In lubricious sense, it is dry after moisturizing sense it is also weaker.Also, in the case of the PPG of comparative example 2, although can be taken a shower
Lubricious sense in use, but solid shape cannot continue, the moisturizing sense after can not being dried.
(about bloating tendency)
(embodiment 2-5)
Then, embodiment 2-5 is illustrated.
The ingredient of the shower cosmetic agent of embodiment 2-5 is as follows.
(embodiment 2)
(a)
91.8 mass % of PEG/PPG-150/35 copolymers
(b1) following 3 ingredients amount to 1.7 mass %
1,2- ethohexadiol, Sensiva SC50, methyl p-hydroxybenzoate
(b2) following 3 ingredients amount to 2.0 mass %
Amino acid, collagen, water
(c)
3.5 mass % of PVA
(d)
1.0 mass % of fragrance
(embodiment 3)
(a)
92.8 mass % of PEG/PPG-150/35 copolymers
(b1) following 3 ingredients amount to 1.7 mass %
1,2- ethohexadiol, Sensiva SC50, methyl p-hydroxybenzoate
(b2) following 3 ingredients amount to 2.0 mass %
Amino acid, collagen, water
(c)
2.5 mass % of PVA
(d)
1.0 mass % of fragrance
(embodiment 4)
(a)
93.8 mass % of PEG/PPG-150/35 copolymers
(b1) following 3 ingredients amount to 1.7 mass %
1,2- ethohexadiol, Sensiva SC50, methyl p-hydroxybenzoate
(b2) following 3 ingredients amount to 2.0 mass %
Amino acid, collagen, water
(c)
1.5 mass % of PVA
(d)
1.0 mass % of fragrance
(embodiment 5)
(a)
94.8 mass % of PEG/PPG-150/35 copolymers
(b1) following 3 at 1.7 mass % of subtotaling
1,2- ethohexadiol, Sensiva SC50, methyl p-hydroxybenzoate
(b2) following 3 at 2.0 mass % of subtotaling
Amino acid, collagen, water
(c)
0.5 mass % of PVA
(d)
1.0 mass % of fragrance
The shower cosmetic agent of above-described embodiment 2-5 is modulated by above-mentioned manufacturing method similarly to Example 1.At this
In a little embodiment 2-5, similarly to Example 1, tested with the test method, and confirm the swelling state in box 50.
In above-described embodiment 2, sense of touch in shower use, it is dry after moisturizing sense and solid shape duration in
Any one not swelling due to water, obtains good result similarly to Example 1.
In embodiment 3- embodiments 5, compared with embodiment 1, embodiment 2, although swelling slightly is seen, compared with
Example 1, comparative example 2 are smaller compared to its swelling.
(embodiment 6-8)
In embodiment 6-8, only shower cosmetic agent is modulated with PEG/PPG copolymers.
That is, in embodiment 6, PEG/PPG-150/35 copolymers are only used, PEG/ is only used in embodiment 7
PPG-200/70 copolymers only use the PEG/PPG-150/35 copolymers and 50 mass % of 50 mass % in embodiment 8
The mixture of PEG/PPG-200/70 copolymers, to modulate shower cosmetic agent.
For obtained shower cosmetic agent, shower cosmetic agent in a manner of similarly to Example 1 out of box 50
Decrement (g) calculates dissolution concentration (ppm), and the results are shown in table 3.
(table 3)
As shown in table 3, in embodiment 6, although the dissolution concentration of cosmetic agent is slightly high at 45 DEG C, at 35 DEG C and
It can inhibit the low concentration as 27.0-27.6ppm at 40 DEG C.It, can be temperature independently by cosmetic agent in embodiment 7
Dissolution concentration inhibit the low concentration as 5.6-10.7ppm.Even if can be temperature independent if in embodiment 8 will
The dissolution concentration of cosmetic agent inhibits the low-down concentration as 13.1-23.0ppm.
Also, it about the shower cosmetic agent of embodiment 6-8, is measured in a manner of similarly to Example 1 in shower use
Sense of touch (lubricious sense), it is dry after moisturizing sense and solid shape duration.As a result, the sense of touch in use and embodiment 1
It is roughly the same.
(embodiment 9-13)
In embodiment 9-13, using PEG/PPG copolymers and PVA, change the content of PVA to modulate shower makeup
Agent.
That is, the PVA of the PEG/PPG-150/35 copolymers and 7 mass % of 93 mass % is used in embodiment 9,
Using the PVA of the PEG/PPG-150/35 copolymers and 3.5 mass % of 96.5 mass % in embodiment 10, in embodiment 11
Using the PVA of the PEG/PPG-150/35 copolymers and 1 mass % of 99 mass %, use 99.5 mass %'s in embodiment 12
The PVA of PEG/PPG-150/35 copolymers and 0.5 mass % uses the PEG/PPG-150/35 of 84 mass % in embodiment 13
The PVA of copolymer and 16 mass %, to modulate shower cosmetic agent.
For obtained shower cosmetic agent, the reduction of the shower cosmetic agent out of box 50 similarly to Example 1
Amount (g) finds out dissolution concentration (ppm), and the results are shown in table 4.
(table 4)
As shown in table 4, in embodiment 9-11 and embodiment 13, a concentration of 6.1-43.3ppm of dissolution of cosmetic agent, and
Compared with the embodiment 6 for having only used PEG/PPG-150/35 copolymers, it can inhibit in low concentration.In embodiment 12, change
A concentration of 22.1-51ppm of dissolution of adornment agent, can not inhibit in low-down concentration compared with Example 6.
Also, about the shower cosmetic agent of embodiment 9-13, the sense of touch in shower use is measured similarly to Example 1
Moisturizing sense after (lubricious sense), drying and solid shape duration.As a result, in embodiment 9-11, the sense of touch in use
It is roughly the same with embodiment 6.In embodiment 12, the moisturizing sense after use and solid shape duration compared with Example 6
It improves, in embodiment 13, solid shape duration improves compared with Example 6.
Therefore, it is mixed into the dissolubility that shower improves shower cosmetic agent to water with the PVA in cosmetic agent, is especially improved
To the dissolubility of warm water, and show that the content of PVA is preferably 0.7-15 mass %.
(embodiment 14 and 15)
In embodiment 14 and 15, using PEG/PPG copolymers, PVA and enamel, to modulate shower makeup
Agent.
That is, using the PEG/PPG-150/35 copolymers of 86 mass %, 13 mass % in embodiment 14
The enamel of PVA and 1 mass %, to modulate shower cosmetic agent.The PEG/PPG- of 86 mass % is used in embodiment 15
The enamel of 200/70 copolymer, the PVA of 13 mass % and 1 mass %, to modulate shower cosmetic agent.As enamel,
Use propylene glycol (wetting agent), pungent ethylene glycol (preservative), Sensiva SC50 (deodorant, antiperspirant), P-hydroxybenzoic acid
The mixture of methyl esters (preservative).
For obtained shower cosmetic agent, the reduction of the shower cosmetic agent out of box 50 similarly to Example 1
Amount (g) finds out dissolution concentration (ppm), and the results are shown in table 5.
(table 5)
As shown in table 5, in embodiment 14, a concentration of 10.2-25.6ppm of dissolution of cosmetic agent and only uses PEG/
The embodiment 6 of PPG-150/35 copolymers is compared, and can be inhibited in low-down concentration.In embodiment 15, cosmetic agent it is molten
Go out a concentration of 3.1-10.3ppm, compared with the embodiment 7 for only using PEG/PPG-200/70 copolymers, can inhibit very
Low concentration.
Also, about the shower cosmetic agent of embodiment 14 and 15, measure in shower use similarly to Example 1
Moisturizing sense after sense of touch (lubricious sense), drying and solid shape duration.As a result, in embodiment 14 and 15, although
The moisturizing sense after sense of touch and use in use is identical as embodiment 6 and 7 respectively, but the two is bloating tendency slightly to be improved,
Solid shape duration is then to reduce.
Claims (9)
1. a kind of shower cosmetic agent, is formed as solid-like, including polyethylene glycol (hereinafter referred to as PEG)/polypropylene glycol (with
Under, referred to as PPG) copolymer and polyvinyl alcohol (hereinafter referred to as PVA) be used as neccessary composition,
The PVA is the partly-hydrolysed PVA that saponification degree is 86-90 moles of %,
The degree of polymerization of the PVA is 1800-2000,
The content of the PVA is 0.5-16 mass %,
The mass ratio of PEG and PPG in the PEG/PPG copolymers are 200/70-150/35,
The content of the PEG/PPG copolymers is 80-97 mass %.
2. shower cosmetic agent according to claim 1, it includes enamels.
3. shower cosmetic agent according to claim 1 or 2, wherein
The PEG/PPG copolymers, PVA or enamel are uniformly dispersed, and are at normal temperatures solid-like.
4. a kind of cosmetic agent box, is accommodated in shower head, wherein
The box has:
Inflow entrance introduces cold water or warm water;
Pipelined channel, with the inflow entrance unicom;And
Cosmetic agent incorporating section has the receiving room of storage cosmetic agent, and has portion of unicom, the portion of unicom by the receiving room and
The pipelined channel unicom makes cold water or warm water by the pipelined channel that can come in and go out the receiving room,
It is accommodated with shower cosmetic agent as claimed in claim 1 or 2 in the cosmetic agent incorporating section.
5. cosmetic agent box according to claim 4, has:
The box has the box shell of tubular;And
In the inner tube that the shaft core position of the box shell is worn,
It is provided with cosmetic agent receiving room between the box shell and inner tube, multiple unicom are equipped in the tube wall of said inner tube
Hole is provided with strainer in the end of downstream side of inner tube.
6. cosmetic agent box according to claim 5, wherein
Overall length in the axial direction of said inner tube arranges the linked hole, and the water-soluble of solid is stored in the cosmetic agent receiving room
Property cosmetic agent, and in cosmetic agent receiving room space is formed in the downstream side of water-soluble cosmetic agent.
7. cosmetic agent box according to claim 5, wherein
The strainer downstream bulging.
8. cosmetic agent box according to claim 5, wherein
The upstream side end of the box shell is provided with valve chamber, the inside connection of the end of downstream side of the valve chamber and said inner tube
It is logical, and it is provided with non-return valve in the valve chamber.
9. cosmetic agent box according to claim 8, wherein
The upstream side end of the cosmetic agent receiving room is configured between the valve chamber and box shell, and around non-return valve
It is closed by the peripheral wall of valve chamber.
Applications Claiming Priority (3)
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JP2013048509 | 2013-03-11 | ||
JP2013-048509 | 2013-03-11 | ||
PCT/JP2013/082052 WO2014141543A1 (en) | 2013-03-11 | 2013-11-28 | Cosmetic for shower use, and cosmetic cartridge |
Publications (2)
Publication Number | Publication Date |
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CN105142609A CN105142609A (en) | 2015-12-09 |
CN105142609B true CN105142609B (en) | 2018-09-28 |
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CN201380074447.7A Active CN105142609B (en) | 2013-03-11 | 2013-11-28 | Shower cosmetic agent and cosmetic agent box |
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JP (1) | JP6280911B2 (en) |
KR (1) | KR20150125717A (en) |
CN (1) | CN105142609B (en) |
HK (1) | HK1218508A1 (en) |
TW (1) | TWI629065B (en) |
WO (1) | WO2014141543A1 (en) |
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KR101942389B1 (en) * | 2017-06-23 | 2019-01-25 | (주)케이비테크놀로지 | Skin Beauty Treatment Material Providing Device |
CN107260586B (en) * | 2017-06-27 | 2020-08-04 | 国珍健康科技(北京)有限公司 | Makeup removing cream gel and preparation method thereof |
FR3068264B1 (en) * | 2017-06-30 | 2021-01-01 | Skinjay | INTELLIGENT SHOWER KIT |
CN109394044B (en) * | 2018-12-13 | 2024-06-04 | 东莞市倍益清环保科技有限公司 | Storage box and shower head |
DE102019105974A1 (en) * | 2019-03-08 | 2020-09-10 | Grohe Ag | Sanitary shower having a jet generator with at least one duck bill valve |
CN110917067B (en) * | 2019-12-04 | 2021-09-21 | 九牧厨卫股份有限公司 | A skin caring cream with high moisture keeping effect for bath and its preparation method |
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Publication number | Priority date | Publication date | Assignee | Title |
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JPH01294616A (en) * | 1988-05-20 | 1989-11-28 | Nippon Korumaa Kk | Aromatic for shower |
JP3703559B2 (en) * | 1996-03-19 | 2005-10-05 | 三菱レイヨン株式会社 | Clean water shower |
JPH10483A (en) * | 1996-06-18 | 1998-01-06 | Tateho Chem Ind Co Ltd | Free chlorine treating agent and its preparation |
JPH11169841A (en) * | 1997-12-15 | 1999-06-29 | Sanden Corp | Water cleaning and sterilizing device |
JP2001186995A (en) * | 1999-10-21 | 2001-07-10 | Kao Corp | Shower implement |
JP3569821B2 (en) * | 2000-10-06 | 2004-09-29 | 株式会社早川バルブ製作所 | Faucet with water purifier |
JP2003053356A (en) * | 2001-08-13 | 2003-02-25 | Ako Kasei Co Ltd | Chlorine treating agent |
JP4149292B2 (en) * | 2002-06-26 | 2008-09-10 | 有限会社寿通商 | Curved water purification cartridge and manufacturing method thereof |
JP2008093188A (en) * | 2006-10-12 | 2008-04-24 | Mrc Home Products Kk | Shower cartridge |
-
2013
- 2013-11-28 WO PCT/JP2013/082052 patent/WO2014141543A1/en active Application Filing
- 2013-11-28 KR KR1020157027815A patent/KR20150125717A/en not_active Application Discontinuation
- 2013-11-28 CN CN201380074447.7A patent/CN105142609B/en active Active
- 2013-11-28 JP JP2015505234A patent/JP6280911B2/en active Active
- 2013-11-29 TW TW102143609A patent/TWI629065B/en active
-
2016
- 2016-06-07 HK HK16106510.0A patent/HK1218508A1/en unknown
Non-Patent Citations (1)
Title |
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"F68和F108水溶液溶胶-凝胶转变过程的流变学研究";汤建凯等;《高等学校化学学报》;20100228;第31卷(第2期);第383页摘要 * |
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CN105142609A (en) | 2015-12-09 |
KR20150125717A (en) | 2015-11-09 |
WO2014141543A1 (en) | 2014-09-18 |
HK1218508A1 (en) | 2017-02-24 |
JPWO2014141543A1 (en) | 2017-02-16 |
TW201434491A (en) | 2014-09-16 |
TWI629065B (en) | 2018-07-11 |
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